Nanoscience and Nanotechnology in SPAIN

Funded by

In collaboration with

Coordinated and edited by

Coordinator
Antonio Correia (Phantoms Foundation)

Design and Layout

Carmen Chacn (Phantoms Foundation) Viviana Estvo (Phantoms Foundation) Maite Fernndez (Phantoms Foundation) Concepcin Narros (Phantoms Foundation) Jos Luis Roldn (Phantoms Foundation)

Experts
Adrian Bachtold - Carbon nanotubes and Graphene Fundaci Privada Institut Catal de Nanotecnologia (ICN), Barcelona Antonio Correia - Introduction - Preface Phantoms Foundation and NanoSpain Network Coordinator, Madrid Viviana Estvo - Introduction Phantoms Foundation, Madrid Ricardo Garca - Scanning Probe Microscopy Instituto de Microelectrnica de Madrid (IMM-CNM, CSIC), Madrid Francisco Guinea - Carbon nanotubes and Graphene Instituto de Ciencia de Materiales de Madrid (ICMM, CSIC), Madrid Wolfgang Maser - Carbon nanotubes and Graphene Instituto de Carboqumica (ICB, CSIC), Zaragoza Rodolfo Miranda - Nanomaterials IMDEA: Madrid Institute for Advanced Studies in Nanosciences (Imdea Nanociencia) Xavier Obradors - Nanomaterials for Energy Materials Science Institute of Barcelona, Barcelona Roberto Otero - Nanomaterials IMDEA: Madrid Institute for Advanced Studies in Nanosciences (Imdea Nanociencia) Francesc Prez-Murano - Nanoelectronics and Molecular Electronics Instituto de Microelectrnica de Barcelona (IMB-CNM, CSIC), Barcelona Emilio Prieto - Nanometrology, nano-eco-toxicology and standardization Spanish Centre of Metrology (CEM), Madrid Stephan Roche - Carbon nanotubes and Graphene Centre d Investigaci en Nanociencia y Nanotecnologa (CIN2, ICN-CSIC), Barcelona Juan Jos Senz - Theory and Simulation Universidad Autnoma de Madrid, Madrid Josep Samitier - Nanomedicine Institute for Bioengineering of Catalonia and Universitat of Barcelona, Barcelona Pedro A. Serena - Introduction Instituto de Ciencias de Materiales de Madrid (ICMM-CSIC), Madrid Niek van Hulst - Nanooptics and Nanophotonics The Institute of Photonic Sciences (ICFO), Barcelona Jaume Veciana - Nanochemistry Instituto de Ciencia Materiales de Barcelona (ICMAB-CSIC), Barcelona Disclaimer The Phantoms Foundation has exercised due diligence in the preparation and reporting of information contained in this book, obtaining information from reliable sources. The contents/opinions expressed in this book are those of the authors and do not necessarily reect views of the Phantoms Foundation.

05 07 19 19 27 37 45 59 67 81 89 95 105 113 113 114 116 117 119 120 123 124 126 129 130 144 148 152 156 160

Preface Introduction Nanoscience & Nanotecnology in Spain: Research Topics

Emerging N&N Centers in Spain

Annex I: Spanish Nanotechnology Network (NanoSpain) / Statistics Annex II: R&D funding Annex III: Publications / Statistics Annex IV: Spain Nanotechnology Companies (Catalogue) Annex V: NanoSpain Conferences Annex VI: Maps for relevant Spanish Initiatives

PREFACE

Considering the fast and continuous evolvements in the interdisciplinary eld of Nanotechnology, Institutions such as the Phantoms Foundation and national initiatives such as the Spanish Nanotechnology Network NanoSpain, should help identifying and monitoring the new emerging elds of research, drivers of interest for this Community, in particular in Spain. Therefore, this second version of the report Nanoscience & Nanotechnology in Spain provides insights by identifying R&D directions and priorities in Spain. Moreover, it aims to be a valid source of guidance, not only for the scientic community but also for the industry. This report covers a wide range of interdisciplinary areas of research and development, such as Graphene, Nanochemistry, Nanomedicine, Carbon Nanotubes, Nanomaterials for Energy, Modelling, etc., and provides insights in these areas, currently very active worldwide and particularly in Spain. It also provides an outlook of the entire Spanish nanotechnology system, including nearly 250 research institutions and over 50 companies. Expected impact of initiatives such as this document is to enhance visibility, communication and networking between specialists in several elds, facilitate rapid information ow, look for areas of common ground between dierent

technologies and therefore shape and consolidate the Spanish and European research communities. I hope you will enjoy reading this document, a collection of ten chapters written by researchers who are at the forefront of their eld in N&N, and look forward to the next edition beginning of 2013 which will explore some new strategic research areas. I would also like to thank all the authors and reviewers for turning this project into reality.

The Editor Dr. Antonio Correia Phantoms Foundation (Madrid, Spain)

> ANTONIO CORREIA Place and date of birth Paris (France), 1966 Education PhD in Materials Science, Universidad Paris 7, 1993 Experience Antonio Correia has over 15 years experience with projects and initiatives related with Nanoscience and Nanotechnology networking. He is author or co-author of 60 scientic papers in international journals and guest Editor of several books. Antonio Correia is currently President of the Phantoms Foundation (Spain) and Coordinator/Board member of several EU funded projects (nanoICT, AtMol, MULT-EU-SIM, nanoCODE, nanomagma, COST BioInspired Nanotechnologies) or initiatives (NanoSpain, M4nano, ICEX Spanish Nanotechnology plan, etc.). Chairman of several conferences (TNT, Nanospain, Imaginenano or Graphene), he is also editor of the Enano newsletter published by the Phantoms Foundation. antonio@phantomsnet.net > VIVIANA ESTVO Place and date of birth Caldas da Rainha (Portugal), 1982 Education Degree in Public Relations & Advertising, INP, 2004. Master Degree in Digital Marketing, EUDE. Experience Works at Phantoms Foundation since January 2010 after a long period working in United Kingdom and Portugal as Marketing Researcher & Communications Account within a broad range of sectors & clients. viviana@phantomsnet.net > PEDRO A. SERENA Place and date of birth Madrid (Spain), 1962 Education Degree in Physical Sciences, Universidad Autnoma de Madrid, 1985 PhD in Physics, Universidad Autnoma de Madrid, 1990 Experience Researcher at the Madrid Materials Science Institute (ICMM) of Spanish National Research Council (CSIC). His research interests include the theoretical study of mechanical and electrical properties of nanosized and low-dimensional systems (metallic surfaces, clusters and nanowires, viral capsids, etc). He is coauthor of 125 articles published in international and national journals covering dierent topics: basic science, scientic dissemination, scientic policy, technologies convergence, prospective studies, sustainable development, etc. He has been editor of the book Nanowires (Kluwer,1997), and co-author of the Unidad Didctica sobre Nanotecnologa (FECyT, Spain, 2009) and author of the book Qu sabemos de la nanotecnologa? (CSIC-La Catarata, 2010). He was coordinator (2000-2003) of the Nanoscience Network and co-founder and co-coordinator (2000-2005) of the NanoSpain Network. Since 2002 to 2005 he was Deputy Director of the ICMM . From 2007 he has been working as Advisor/Assistant of the Spanish Ministry for Science and Innovation to manage the Strategic Action in Nanoscience and Nanotechnology.From 2006 is secretary of the Scientic Advisory Board of the Madrid Science Park and from 2010 is member of the CSIC Scientic Advisory Committee. pedro.serena@icmm.csic.es

INTRODUCTION

1. Introduction Nanoscience and Nanotechnology (N&N) have become a rapidly growing research and development (R&D) eld that is cutting across many traditional research topics. Nowadays the ability to construct nano-objects and nanodevices provides novel advanced materials and astonishing devices and will lead to the future development of fully functional nano-machines and nano-materials, virtually having an eect on every manufactured product, the production and storage of energy, and providing a host of medical applications ranging from in situ and real time diagnostics to tissue regeneration. N&N are more than simply the next frontier in miniaturization, since the properties of materials and devices dramatically change when their characteristic dimensions moves down the nanoscale, revealing an entirely new world of possibilities. 2. Potential nanotechnology applications and their social impact The evaluation of the expected impact of a technology wave is always an uncertain business. Yet there seems little doubt that the very nature of nanotechnology will precipitate important changes, the only question is its timetable. In the case of N&N, perhaps, the rst measurable impact has been its eect on the media. In a decade everything 'nano' has gone from non-

existent to being object of extensive articles and reports in scientic and non-scientic journals, as well as to be a favorite discussion topic in web pages, forums and blogs in Internet. When we speak about social impact, we are referring to the capacity of Nanotechnology to generate applications and devices that will induce true changes in our daily life, our jobs, our homes, our health, etc. N&N will fundamentally restructure the technologies currently used for manufacturing, medicine, security, defence, energy production and storage, environmental management, transportation, communication, computation and education. Given the multidisciplinary character of N&N, the list of expected application areas is very long. The broad scope of N&N applications will aect dierent aspects of the activity of human beings. Nevertheless, we can highlight that many of these applications are focused on the improvement of human health, whereas others will facilitate a more sustainable economic development allowing the optimization of resources and diminishing environmental impact. 3. Nanotechnology Research Funding Nanoscience, transformed in Nanotechnology, is taking now its rst steps outside the laboratories and many small and large companies are

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launching a rst wave of nanoproducts into the markets. However, the actual power of Nanotechnology resides in an immense potential for the manufacture of consumer goods that, in many cases, will not be commercialized before a couple of decades, thus bringing tangible and promising results for the economy. Because this huge expected economic impact, nanotechnology has roused great interest among the relevant public and private R&D stakeholders of the worlds most developed countries: funding agencies, scientic policymakers, organisations, institutions and companies. N&N represent one of the fastest growing areas of R&D. In the period of 1997-2005 worldwide investment in Nanotechnology research and development has increased approximately nine times, from US$ 432 million to US$ 4200 million. This represents an average annual growth rate of 32%. A great example is the National Nanotechnology Initiative (NNI) that was established in 2000 and links 25 federal agencies closely related to activities in N&N. NNI budget allocated to the federal departments and agencies increased from US$ 464 million in 2001 to approximately US$ 1700 million in 2009. For 2011 the funding request for nanotechnology research and development (R&D) in 15 federal departments and agencies is US$ 1760 million, reecting a continuous growth in strategic collaboration to accelerate the discovery and deployment of nanotechnology. In addition to the federal initiative, an important eort has been carried out by the dierent US state governments, as well as companies (Motorola, Intel, HewlettPackard, IBM, Amgen, Abbot Lab., Agilent, etc). Industrialized Asian countries have promoted the development of Nanotechnology from the industrial and governmental sectors, with investments similar to those of USA. Countries as Taiwan and Korea have made a great eort to keep their current privileged positions in the

control of Nanotechnology know-how. According to Mihail Roco, Japan increased their budget from US$ 245 million in 2000 to US$ 950 million in 2009, proving a signicant rising of the investment from the Japanese Government. Taiwanese, Japanese and South Korean companies are leading the Nanotechnology investments in their respective countries. In the meantime, China has become a key player in the Nanotechnology eld, leading sectors as the fabrication of nanoparticles and nanomaterials. Countries as Israel, Iran, India, Singapore, Thailand, Malaysia and Indonesia have launched specic programmes to promote the use of Nanotechnologies in many industrial sectors with local or regional impact (manufacture, textile, wood, agriculture, water remediation, etc). Europe has intensively promoted Nanotechnology within the VI (FP6) and the VII (FP7) Framework Programme through thematic Areas denominated NMP1 and ICT2. During the period of 2003-2006 the budget for NMP was 1429 million Euros and a remarkable increase of 3475 million Euros for funding N&N over the duration of FP7 (2007-2013). Theres a proven commitment of the EU to strengthen research in Europe. Initiatives involving not only increased investment, but also stronger coordination and collaboration between all stakeholders like the FET agship (ICT) are being implemented. In order to improve the competitiveness of European industry, to generate and ensure transformation from a resource-intensive to a knowledge-intensive industry were created the FET Flagships Initiatives. FET-Proactive acts as a pathnder for the ICT program by fostering novel non-conventional approaches, foundational research and supporting initial developments on long-term research and technological innovation in selected themes. Under the FP7 program were created AMOL-IT, nanoICT and Towards Zero-Power ICT projects in order to focus resources on visionary and

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challenging long-term goals that are timely and have strong potential for future impact. There has been a boom of European initiatives dedicated to develop and popularize Nanotechnology and this area maintains its outstanding role in the FP7 Program. Among the EU members, Germany stands right at the forefront of international Nanoscience and is considered as a key location for nano research. The Federal Government by exceptional funding programs is helping to turn Germany into the leading nano spot. In 2008 about 430 million Euros were invested by public funding in Nanotechnology. Nowadays, around 740 companies work on the development, application and distribution of nanotechnology products. Following similar long term strategies, on December 2009, French Government unveiled a 35000 million Euros national bond to prepare France for the challenges of the future. The spending spree over the coming years contemplates higher education and research as the main priorities, among others. Part of this amount will be applied to create new Campus of Excellence, develop research teams, boost competitiveness and increase eorts in biotechnology and nanotechnology. The (2011-2016) consortium in NanoNextNL3 Netherlands which supports research in the eld of nano and microtechnology is another great example of the eorts made by the European countries. This initiative embrace 114 partners and the total sum involved is 250 million Euros, half of which is contributed by the collaboration of more than one hundred businesses, universities, knowledge institutes and university medical centres and the other half by the Ministry of Economic Aairs, Agriculture and Innovation. NanoNextNL is the successor of NanoNed and MicroNed programmes which were also greatly supported. In the same line, we must mention the Austrian NANO Initiative, a multi-annual funding programme for N&N that

EU authorities have also taken into account serious concerns on Nanotechnology, appearing in diverse social and economic forums during the last decade, in relation with its possible environmental and health eects. These nondesired drawbacks would provide a negative social perception on the development on Nanotechnology and could lead to an unexpected cut of private and public investments, with the subsequent delay in the arrival of the bunch of promised goods, devices and materials. In order to allow a coherent (rational, sustainable, nonaggressive, etc) development of Nanotechnology, the EU has promoted basic and applied research on nanoecotoxicology and dierent studies on social perception on N&N. Simultaneously, several EU Departments have launched initiatives to improve the communication and dissemination among population on the future advances and risks that Nanotechnology will bring. A good example is the European Project NanoCode5, funded under the Program Capacities, in the area Science in Society, within the 7th Framework Program (FP7) which started in January 2010 in order to implement the European Code of Conduct for Responsible Nanosciences & Nanotechnologies. In addition, EU has also promoted the generation of knowledge based on Nanotechnology emphasizing the role of this techno-scientic area

INTRODUCTION

coordinates NANO measures on the national and regional levels and is supported by several Ministries, Federal provinces and Funding institutions, under the overall control of the BMVIT Federal Ministry for Transport, Innovation and Technology. The orientation and the structure of the Austrian NANO Initiative have been developed jointly with scientists, entrepreneurs and intermediaries. The Austrian NANO Initiative4 has funded nine RTD project clusters involving more than 200 Austrian companies and research institutions.

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as foundation for future convergence with other disciplines such as Biotechnology, Medicine, Cognitive Science, Communications and Information Technologies, Social Sciences, etc. 4. Nanotechnology in Spain: a successful history

At the end of 90s, Spain had not any institutional framework nor initiative pointed towards the support and promotion of R&D in Nanotechnology. This fact pushed the scientic community to promote several initiatives to strengthen research in Nanotechnology and, at the same time, to raise the awareness of Public Administration and industry about the need to support this emergent eld. Among the initiatives that emerged in Spain in this last decade we can highlight the creation of several thematic networks with a strong multidisciplinary character. These networks have

enabled communication between scientic communities and dierent areas, improving the interaction between Spanish groups and improving the visibility of this community. NanoSpain network6 is the clearest example of self-organization of scientists that helped to promote to the authorities and the general public the existence of this new knowledge, in order to generate and achieve competitive science, which can result into high value added products in the near future. NanoSpain network comprises nearly 300 R&D groups (See Annex I) from universities, research centers and companies, distributed throughout the country. These groups respresent a research task force formed by more than 2000 scientists working in N&N. Despite being the meeting point of the continuously increasing Spanish nanotechnology community, NanoSpain network has received little support from Spanish Administration in contrast to those networks established in other countries.

INTRODUCTION

Figure 1. Regional Distribution of research groups NanoSpain Network. (As of March 31, 2010).

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In early 2003 the initiatives launched by the scientic community (networks, workshops, conferences) related to nanotechnology led to the incorporation of the Strategic Action in Nanoscience and Nanotechnology in the National Plan R+D+I for the 2004-2007 period. This Strategic Action has had its continuity in the current National Plan (2008-2011), also including topics related to new materials and production technologies. Both strategic actions maintained an increasing rate of investment in nanotechnology in the period of 2004-2009. For example, the eort made by the General State Administration (GSA) in the implementation of N&N has been over 82 million Euros in 2008. During the 20042007 period the Strategic Action focused on small scale projects whereas during the 2008-2011 period the funding was mainly allocated to large

Under the policies of the General State Administration (GSA), the Ingenio 2010 program through programs such as CENIT, CONSOLIDER and AVANZA, allowed many economic resources in strategic areas such as nanotechnology. Currently, 8 CONSOLIDER and 9 CENIT projects are related to nanotechnology, with a total GSA funding of 37.9 and 127.8 million Euros, respectively. In the case of CENIT projects, participating companies provided an additional amount of 127.8 M . Over the next few years we expect to see the results of these initiatives through several indicators. Another important initiative is the Biomedical Research Networking center in Bioengineering, Biomaterials and Nanomedicine9 (CIBER-BBN), a consortia, created under the leadership of the Carlos III Health Institute (ISCIII) to promote research excellence in bioengineering and biomedical imaging, biomaterials and tissue engineering and nanomedicine, diagnosis and monitoring and related technologies for specic treatments such as regenerative medicine and nanotherapies. In addition to GSA strategies, the regional governments expressed with more or less

Table 1. Fiscal eort made by Spanish government in the eld of Nanoscience and Nanotechnology in the year 2008 (Source: Ministry of Science and Innovation of Spain).

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Another Spanish initiative, which emerged from the scientic community and has become an international benchmark, is the celebration of eleven consecutive editions of the conference "Trends in Nanotechnology"7. These meetings, a true showcase of Spanish nanoscience and nanotechnology, attracted the most prestigious international researchers, improving the visibility of Spanish scientists. The international event, ImagineNano8, is also a step further, a meeting that gather nearly 1500 participants from all over the world, combining within the same initiative a set of high impact conferences and an industry exhibition with more than 160 institutions/companies.

scale initiatives as the building of new R&D centers or public-private consortia and platforms. The International Campus of Excellence program was discussed in 2008, rst staged competitively in 2009 and in 2010 became rmly established and aims to put major Spanish universities among the best in Europe, promoting international recognition and supporting the strengths of the Spanish university system. The program is managed by the Ministry of Education in collaboration with other ministries and supported by the Autonomous Communities. In many cases, as the Excellence Campus of Universidad Autnoma de Madrid or the Universidad Autnoma de Barcelona include remarkable activities related to the promotion of N&N.

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Figure 2. Emerging N&N Centers in Spain.

emphasis their interest in nanotechnology, including this topic in its regional plans of R&D and encouraging the creation of new regional networks. However, most palpable manifestation of the widespread interest in nanotechnology is the establishment of new research centers as joint projects of the Ministry of Science and Innovation, Autonomous Communities and Universities. (See Annex VI and Fig. 2). The International Iberian Nanotechnology Laboratory10 (INL) is the result of a joint decision of the Governments of Portugal and Spain, taken in November 2005 whereby both countries made clear their commitment to a strong cooperation in ambitious science and technology joint ventures for the future. The new laboratory is established by Portugal and Spain, but in the future will be open to the

membership of other countries of Europe and other regions of the world. Some of the centers indicated in Fig. 2 are under construction and are expected to be fully operational during the decade 2010-2020. This set of centers, along with those already existing in the public research organizations, the network of Singular Scientic and Technological Infrastructures forms a system of huge potential forms research in nanoscience and nanotechnology. The task of knowledge generation must be completed by the technology transfer oces of universities and public research organizations, the Technology Centers, and the many Science and Technology Parks that have been successfully implemented in Spain11. Also emerge thematic "nano-networks" and nanoplatforms oriented to productive sectors as

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These strategies for generation and transfer of knowledge are reinforced by other complementary activities aimed at both the internationalization of our scientic-technological results and the dissemination of science. As an example of the internationalization, the Spanish Institute of Foreign Trade (ICEX), through its "Technology Plan" in Nanotechnology (coordinated by Phantoms Foundation) encourages external promotion activities of research centers and companies, enabling the participation of Spain with pavilions and informative points in several international exhibitions as Nanotech Japan (2008-2011), one of the most important events in nanotechnology, NSTI fair (2009) in U.S. and Taiwan Nano (2010)18. More recently, a catalogue of N&N companies in Spain was compiled by Phantoms Foundation and funded by ICEX and gives a general overview of the enterprises working in this eld. Since the year of 2000 until 2010, were created 36 companies mainly in nanomaterials, nanocomposites, nanobio and nanoparticles. So far 60 companies performing R&D in nanoscience and nanotechnology are listed and is predicted a signicant increase in the upcoming years. In terms of outreach eorts we can mention several initiatives. On one hand the edition of the rst book in N&N issued by the Spanish Foundation for Science and Technology (FECYT),

One could say that in this last decade we have seen an explosion of initiatives in the eld of nanotechnology. All initiatives represent a clear commitment that Spain is situated in the medium term between the group of countries that can lead the change towards a knowledgebased society. However, it is necessary to maintain a constant tension to strengthen the settlement of all initiatives. The short-term challenge is to continue the investement, despite being in an economic crisis, and improve coordination of all players involved in the R+D+I. The next decade will conrm whether eorts have been sucient to be amongst the most advanced economies, fullling the expectations for nanotechnology as an engine of Spanish industry in 2020. Everything achieved so far has required a great eort, but still we have a R&D system relatively weak compared with those countries which we want to look like. Any change in the sustained investment policies in our R&D system can take us back several years, as budget cuts are announced to overcome this period of crisis they can also be very harmful in an

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RENAC12 (Network for the application of nanotechnologies in construction and habitat materials and products), SUSCHEM13 (Spanish Technology Platform on Sustainable Chemistry), GNESIS14 (Spanish Technology Platform on Nanotechnology and Smart Systems Integration), NANOMED15 (Spanish Nanomedicine Platform), MATERPLAT16 (Spanish Technological Platform on Advanced Materials and Nanomaterials) or Fotonica2117 (The Spanish Technology Platform of Photonics), among many others.

designed to spread among teachers in secondary and high school education along with books devoted to N&N dissemination that have been recently issued. On the other hand, events as Atom by Atom or Passion for Knowledge disclose the progresses, challenges and implications of various nano-areas to a broad and general audience. Furthermore, initiatives as the SPMAGE international contest19 of SPM (Scanning Probe Microscopy) images or the exhibition A walk around the nanoworld are succesful initiatives to disseminate N&N. Recently, an Iberoamerican Network for Dissemination and Training in N&N (NANODYF)20 has been funded by the Iberoamerican Programme for Science and Technology (CYTED) in order to promote formal and non-formal education of N&N in Iberoamerican countries where more than 460 million people communicate in Spanish.

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emerging issue as nanotechnology. We hope these cuts are punctual and that soon will regain the road of support R&D&I. In the meantime, before recovering the previous momentum, we need to implement new strategies intended to keep the path we started ten years ago under a more restrictive economic scenario. These strategies must be based in few ingredients, including among others: (i) the stimulus of the dialogue between Spain Ministries and Regional Goverments, on one side, and scientic community using existing networks that must be suitably funded on the other; (ii) the increasing coordination of research centres and large scale infrastrutures in order to optimize the access to scientic services of public and private groups; (iii) to enhace publicprivate cooperation through Technology Platforms, Industry Networks and Science and Technology Parks; (iv) an actual support to small N&N spin-os emerging from research centres, (v) the formation of a new generation of PhD students and technicians highly skilled for multidisciplinary research through specic training programs (Master and PhD courses); and (vi) the involvement of society through well designed dissemination activities using emerging communication technologies. 5. Conclusions Nanoscience and Nanotechnology represent scientic-technical areas that in less than two decades have gone from being in the hands of a reduced group of researchers who glimpsed their great potential, to constitute one of the recognized pillars of the scientic advance for the next decades. The ability to manipulate the matter on atomic scale opens the possibility of designing and manufacturing new materials and devices of nanometric size. This possibility will alter the methods of manufacturing in factories, allowing for greater process optimization and

INTRODUCTION

automation, and therefore contributing to global sustainable development. On the other hand, the nanotechnological revolution will speed up the seemingly unstoppable expansion of the information technologies, and causing the globalization of the economy, the spreading of ideas, the access to the dierent sources of knowledge, the improvement of the educative systems, etc, to increase vertiginously. Finally, the irruption of the Nanotechnologies will directly aect human beings by substantially improving diagnosis and treatment of diseases, and also our capacities to interact with our surroundings. Right now we are facing a powerful scientic paradigm with a multidisciplinary character, where Chemistry, Engineering, Biology, Physics, Medicine, Materials Science, and ModellingComputation converge. Establishing links between the scientic communities, looking for contact points and promoting the existence of multidisciplinary groups, where imaginative solutions to nanoscale problems are forged, becomes now essential. Further reading Introduction C. P. Poole and F. J. Owens, Introduction to the Nanotechnology, Wiley-VCH, Weinheim (2003). R. Waser (Ed.) Nanoelectronics and Information Technology, Wiley-VCH, Weinheim (2003). M. Ventra, S. Evoy, J.R. Hein (Eds.), Introduction to Nanoscale Science and Technology, Series: Nanostructure Science and Technology, Springer (2004). A. Nouaihat, An Introduction to Nanosciences and Nanotechnology , Wiley-ISTE (2008). G. L. Hornyak, J. Dutta, H.F. Tibbals and A. Rao, Introduction to Nanoscience, CRC Press (2008).

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Funding Marks & Clerk, Nanotechnology, Report (2006). www.nano.gov/about-nni/what/funding The long view of Nanotechnology development: The national Nanotechnology Initiative at ten years, Mihail Roco (2011) www.nsf.gov/crssprgm/nano/reports/nano2 /chapter00-2.pdf Some Figures about Nanotechnology R&D in Europe and Beyond, European Commission, Research DG ftp://ftp.cordis.europa.eu/pub/ nanotechnology/docs/nano_funding_data_ 08122005.pdf UE FP7 (NMP theme): http://cordis.europa.eu/fp7/cooperation/ nanotechnology_en.html EU FP7 Nanotechnology funding opportunities: http://cordis.europa.eu/ nanotechnology/src/eu_funding.htm EU FP7 Technological Platforms: http://cordis.europa.eu/technologyplatforms/ home_en.html FET Flagships http://cordis.europa.eu/fp7/ict/ programme/fet/agship/ EU-FP7 (ICT-FET) proactive initiative (nano ICT - NANO-SCALE ICT DEVICES AND SYSTEMS): http://cordis.europa.eu/fp7/ict/fetproactive/nanoict_en.html http://cordis.europa.eu/search/ index.cfm?fuseaction=prog.document& PG_RCN=8737574

Nanotechnology in Spain I+D+I National Plan 2008-2011 http://publicacionesopi.micinn.es/docs/ PLAN_NACIONAL_CONSEJO_DE_ MINISTROS.pdf P.A. Serena, Report on the implementation of the Action Plan for Nanosciences and Nanotechnologies in Spain (2005-2007)", Ocina Europea Micinn: www.oemicinn.es/programa-marco/ cooperacion/nanociencias-nanotecnologiasmateriales-y-nuevas-tecnologias-de-laproduccion/documentos-de-interes/informe-de-la-implementacion-del-plan-de-accion-de-nanociencias-y-nanotecnologias-par a-el-periodo-2005-2007-en-espana P. A. Serena, A survey of public funding of nanotechnology in Spain over 2008. Ministry of Science and Innovation report to the European Commission. www.oemicinn.es/content/ download/1122/7623/le/ REPORT2008-First-Implementation-PlanFINAL-INL.pdf

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S. Lindsay, Introduction to Nanoscience, Oxford University Press (2009). M- Pagliaro, Nano-Age: How Nanotechnology Changes our Future, Wiley-VCH (2010). S.H. Priest, Nanotechnology and the Public: Risk Perception and Risk Communication (Perspectives in Nanotechnology), CRC Press (2011).

Research in Germany: www.research-in-germany.de/dach portal/en/downloads/download-les/ 9434/welcome-to-nanotech-germany.pdf www.research-in-germany.de/researchareas/68296/nanotechnology.html Paris plans science in the suburbs: www.nature.com/news/2010/101020/full/ 467897a.html French research wins huge cash boost: www.nature.com/news/2009/091215/ full/462838a.html http://ec.europa.eu/health/ph_risk/ documents/ev_20040301_en.pdf A. Nordmann, Converging Technologies Shaping the Future of European Societies: www.ntnu.no/2020/nal_report_en.pdf

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www.educacion.gob.es/campusexcelencia.html www.micinn.es/portal/site/MICINN/ menuitem.7eeac5cd345b4f34f09dfd1001432ea0/? vgnextoid=b0b841f658431210VgnVCM1000 001034e20aRCRD (Technological Platforms) J.A. Martn-Gago et al. Teaching Unit Nanoscience and Nanotechnology. Among the science ction of the present and the future technology, Foundation for Science and Technology (FECYT), Madrid 2008 Event Atom by Atom (San Sebastian, Spain): http://atombyatom.nanogune.eu/ Event Passion for knowledge (San Sebastian, Spain): www.dipc10.eu/es/passion-forknowledge Industrial Applications of Nanotechnology in Spain in 2020 Horizon, Fundacin OPTI and Fundacin INASMET-TECNALIA, Madrid. (2008). The book can be downloaded free from: www.opti.org

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www.genesisred.net/index.php www.nanomedspain.net www.materplat.es www.fotonica21.org www.phantomsnet.net/nanotech2008/; www.phantomsnet.net/nanotech2009/; www.phantomsnet.net/nanotech2010/; www.phantomsnet.net/NSTI2009/; www.phantomsnet.net/Taiwan2010/ www.icmm.csic.es/spmage/ www.nanodyf.org

References
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FP6 Thematic Area denominated Nanotechnologies and nano-sciences, knowledge-based multifunctional materials and new production processes and devices and FP7 denominated Nanosciences, Nanotechnologies, Materials and new Production Technologies ICT: Information and Communication Technologies www.nanonextnl.nl www.nanoinitiative.at www.nanocode.eu www.nanospain.org www.tntconf.org www.imaginenano.com www.ciber-bbn.es www.inl.int www.apte.org www.nano-renac.com www.suschem-es.org

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> JAUME VECIANA Place and date of birth San Salvador (Rep. El Salvador), 1950 Education Degree in Chemical Science, Univ. Barcelona, June 1973. Doctor in Chemistry, Univ. Barcelona, November 1977. Experience Main research activities are focused on functional molecular materials with metallictransport and magnetism-properties, supramolecular materials and to the development of molecular nanoscience and nanotechnology. Research is also aimed towards the development of new processing methods for structuring functional molecular materials as nanoparticles and their patterning on surfaces. Also activities in Nanomedicine are currently developed. vecianaj@icmab.es

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1. Introduction Nanochemistry is the term generally used to gather all activities of Nanoscience and Nanotechnology (N&N) having in common the use of the traditional concepts, objectives and tools of Chemistry. Accordingly, Nanochemistry deals with the design, study, production, and transformation of basic materials into other often more complex products and materials that show useful properties due to their nanoscopic dimensions. This area of research has the potential to make a signicant impact on our world since it has an enabling character underpinning technology clusters such as materials and manufacturing. Application areas include construction, cosmetics, pharmaceutical, automotive, and aerospace industry, as well as polymer additives, functional surfaces, sensors and biosensors, molecular electronics, and targeted drug release. It is just in this area of research where one of the most important and commonly used approaches of N&N, the bottom-up-approach, comes from, whose objectives are to organize the matter at the nanoscale from atoms or molecules with the purpose of obtaining new properties or applications. Due to the transversal character of Nanochemistry, it is expected that the research

in this area will contribute to solving multiple societal issues and will have an enormous impact in many aspects and activities of our lives; especially those related with: a) Energy b) Information and Communication Technologies c) Healthcare d) Quality of Life e) Citizen Protection f) Transport Indeed, activities in this discipline will enable our European society to become more sustainable, due to new and improved products and processes that supply new and existing products more eciently. Moreover, it is anticipated that the economical and social impacts of Nanochemistry in our society will be very high both in terms of generating greater wealth and larger economical revenues, improving our trade balances, as well as in the generation and maintaining employments because it will push and renew traditional activities of chemical industry in Europe. This aspect is important because the chemical industry is one of the pillars of the European economy. It is ubiquitous and is a signicant factor in the improved quality of life enjoyed by European citizens today.

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2. State of the Art (recent advances, etc.) In order to analyse the state of the art of this area and describe the recent advances, over the 2007-2009 period, a search was made in the ISI Web of Knowledge (Web of Science) crossing the terms chem* and nano*. This search gave 36.400 results corresponding to papers that appeared in journals devoted to general science, chemistry, nanoscience, materials science, and physics. A careful analysis of the most cited articles of this search permitted to localize those topics inside Nanochemistry that have received more attention among the scientic community. A list of those topics, randomly ordered, is as follows:
Figure 1. SEM image of a drug processed as a particulate material for controlling its delivery. Courtesy of NANOMOL, ICMAB (CSIC)-CIBERBBN.

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Self-assembled organizations in 0-, 1-, 2-, and 3-Dimensions. Hierarchical functional organizations. supramolecular

According with the vision paper of the European Technology Platform for Sustainable Chemistry (SUSCHEM), The vision for 2025 and beyond, the EU is a leading global chemicals producing area, with 32% of world chemicals production. This sector contributes 2.4% to European Union GDP and comprises some 25,000 enterprises in Europe, 98% of these are SMEs, which account for 45% of the sector's added value. The chemical industry of the 25 State Members of EU currently employs 2.7 million people directly, of which 46% are in SMEs, with many times this number employed indirectly. Consequently, N&N could help to boost European research, development and innovation in chemical technologies becoming a major determining factor to secure the sector's competitiveness and consequently the overall competitiveness. Thus, the future activities in Nanochemistry will be of the utmost importance for our lives and economy.

Studies on molecular dynamics on surface reactions. Basic studies on interfacial structural aspects of small molecules. Synthesis and studies motors/machines/valves. Design, preparation nanoreactors. of molecular study on

and

Design and preparation of metal-organic frameworks with new properties. Chemically modified surfaces for microfluidics. Nanogels obtained techniques. by polymerization

Catalytic activity studies of metallic clusters. Chirality enhancement of surfaces or nanotubes. New methods for preparation of nanocrystals /nanowires/nanotubes/nanovesicles.
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Chemically modified surfaces / nanofibres / nanotubes and their applications. Nanofabrication based on layer-by-layer assembly techniques. Polymers with responsive properties to external stimuli. Nanoparticles for being used as sensors, medical imaging and therapy. Nanostructured materials for gas storage applications. Nanostructured materials for photovoltaics and photonics. Nanostructured applications. materials for energy

Molecule-based techniques for printing. Plasmon resonance studies of functionalized surfaces/particles. Electron transport in molecular junctions and in nanotubes and graphenes. Nanoparticles and nanostructrued materials for sensing Hg2+ ions in water. Preparation and functionalization polymeric dendrons and dendrimers. of

Synthesis and characterizaton of monodisperse structured (hollow, core-shell, capsules, etc.) nanoparticles. 3. Most relevant international papers in the area appearing during 2007-2009 The most cited papers found in the above mentioned searching using the terms nano* and chem* are the following: Synthetic molecular motors and mechanical machines. Kay, ER; Leigh, DA; Zerbetto, F., Angew. Chem. Int. Ed., 46, 72-191 (2007). Titanium dioxide nanomaterials: Synthesis, properties, modifications, and applications. Chen, X; Mao, SS, Chem. Rev., 107, 2891-2959 (2007). Chemically derived, ultrasmooth graphene nanoribbon semiconductors. Li, XL; Wang, XR; Zhang, L; Lee, SW; Dai, HJ, Science, 319, 1229-1232 (2008). Detection of individual gas molecules adsorbed on graphene. Schedin, F; Geim, AK; Morozov, SV; Hill, EW; Blake, P; Katsnelson, MI; Novoselov, KS, Nature Mater, 6, 652-655 (2007). 'Click' chemistry in polymer and materials science. Binder, WH; Sachsenhofer, R, Macromol. Rapid Comm., 28, 15-54 (2007).
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Nanostructured materials for drug delivery and targeting purposes. Self-assembled nanoprobes for NMR imaging. Synthesis, functionalization, and application of magnetic nanoparticles. Mesoporous materials for drug delivery. Drug encapsulation in nanostructured objects for biomedical applications. DNA hybridized materials for use in medical and sensing applications. Basic studies on cell internalization of nanostructured organizations. Functionalization of quantum dots for cellular imaging. Positioning and manipulating enzymes, nucleic acids, and protein-based objects in nanoreactors. Synthesis and studies of graphene and derivatives. Click chemistry and its applications. Modification of surface wetting properties.

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Polyoxometalate clusters, nanostructures and materials: From self assembly to designer materials and devices. Long, DL; Burkholder, E; Cronin, L, Chem. Soc. Rev., 36, 105-121 (2007).

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Synthesis of tetrahexahedral platinum nanocrystals with high-index facets and high electro-oxidation activity. Tian, N; Zhou, ZY; Sun, SG; Ding, Y; Wang, ZL, Science, 316, 732-735 (2007). Localized surface plasmon resonance spectroscopy and sensing. Willets, KA; Van Duyne, RP, Ann. Rev. Phys. Chem., 58, (2007). Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide. Stankovich, S; Dikin, DA; Piner, RD; Kohlhaas, KA; Kleinhammes, A; Jia, Y; Wu, Y; Nguyen, ST; Ruoff, RS, Carbon, 45, 1558-1565 (2007). Processable aqueous dispersions of graphene nanosheets. Li, D; Muller, MB; Gilje, S; Kaner, RB; Wallace, GG, Nature Nanotechnology, 3, 101-105 (2008). New directions for low-dimensional thermoelectric materials. Dresselhaus, MS; Chen, G; Tang, MY; Yang, RG; Lee, H; Wang, DZ; Ren, ZF; Fleurial, JP; Gogna, P, Adv. Mater., 19, 1043-1053 (2007). Nanoelectronics from the bottom up. Lu, W; Lieber, CM, Nature Mater, 6, 841-850 (2007). Molecular architectonic on metal surfaces Barth, JV, Ann. Rev. Phys. Chem., 58, 375-407 (2007). Colorimetric detection of mercuric ion (Hg2+) in aqueous media using DNAfunctionalized gold nanoparticles. Lee, JS; Han, MS; Mirkin, CA, Angew. Chem. Int. Ed., 46, 4093-4096 (2007). Analysis of phosphorylation sites on proteins
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from Saccharomyces cerevisiae by electron transfer dissociation (ETD) mass spectrometry. Chi, A; Huttenhower, C; Geer, LY; Coon, JJ; Syka, JEP; Bai, DL; Shabanowitz, J; Burke, DJ; Troyanskaya, OG; Hunt, DF, Proc. Nat. Acad. Sci. USA, 104, 2193-2198 (2007). 4. Actuations to undertake in Spain during 2010-2013 It would be convenient that actions to promote and boost Nanochemistry in Spain in the next years follow the general directions undertaken by the most important European initiatives. There is a prospective roadmap, performed at the European level by the European Technology Platform (ETP) for Sustainable Chemistry (SusChem) that appeared in its Strategic Research Agenda (SRA), where products and technologies are given, together with their short-, mid- and long-term priorities and the expected market volume. Most of such products and technologies can be beneted from advances in Nanochemistry and, therefore, grouped by socio-economical sectors are detailed below: Energy Products: Materials for hydrogen storage and transport, fuel cells and batteries, conducting polymers, superconductors and semiconductors, light emitting diodes, solar cells, and thermal insulating materials. Technologies: Scale-up processes for the production of advanced materials, analytical technologies for the quality control of advanced materials, and process development and control technology. Information and Communication Technologies Products: Supercapacitors, luminescent materials

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Technologies: Scale-up processes for the production of advanced materials, process development and control technology, technologies which take advantage of structure-property relationships and interface eects, high-power technologies, miniaturization, and biotechnological production processes of molecular components.

Technologies: Formulation engineering of micro, nanostructured emulsions/ dispersions and particulate products for controlled release, generic methods for introduction of chiral centers, in-silico prediction of drug pharmacokinetics, highthroughput screening technologies, new MRI, NMR and spectroscopy techniques, scale-up processes for the production of advanced materials, innovative fermentation processes for novel antibiotics production, biocatalytic production of pharma building blocks. Quality of Life Products: Devices for ecient lightening, environment sensors, membranes for treatment of drinkable water, materials for acoustic and thermal insulation, smart electrochromic devices, interactive functional textile devices, intelligent materials for packaging, and food quality sensors, enzymes for new detergents and for removal of carcinogenic compounds in food, food tracking systems.

Figure 2. Weaved textile with metallic conducting properties based on a nanocomposite polymeric material. Courtesy of NANOMOL, ICMAB (CSIC)-CIBER-BBN.

Technologies: Sensing materials and techniques,

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for displays, OLEDs, E-paper, molecular electronics, molecule-based for spintronics, semiconducting materials, conducting polymers, materials with enhanced mobility, materials for storage and transport of information and for holography, batteries, eco-ecient electronic devices, optical materials, pico-second molecular switches, and portable devices for hydrogen transport.

Healthcare Products: Tumor therapy, targeted drug-delivery, bone reconstruction, tissue engineering. New antibiotics by novel microorganisms, preparation of antibodies, peptides, and proteins by bioprocesses, medical devices, Smart delivery systems, tissular engineering, instant diagnosis, functional textiles, and lab-on-a-chip devices.

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formulation of products with dened particulate structure, adapting intensied process equipment, scale-up processes for the production of advanced materials, process development and control technology.

technology-platforms/ individual_en.html where it is also possible downloading their strategic research agendas and implementation action plans. Many of such ETPs have created mirror platforms in Spain which are currently developing intense activities to boost their respective areas in our country. Probably those ETPs whose interests are closer to Nanochemistry activities and will benet from new advances in this area are the following: Advanced Engineering Technologies (EuMaT); www.eumat.org Materials and

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Citizen Protection Products: Devices for biometric identication, smart cards, protecting tissues, superhydrophobic bers, conducting and optical bers, alarm devices, thermo-chromic windows, functionalized polymers and surfaces as recognition layers, electrostrictive materials, and pressure sensitive carpets. Technologies: Scale-up processes for the production of advanced materials, sensing materials and techniques, and process development and control technology. Transport Products: Devices for instantaneous diagnosis and attending car drivers, trac management sensors, improved safety devices, materials for recyclable and biodegradable vehicles, materials for constant repair, silent car & road, instant diagnosis/sensors, enhanced safety for transportation systems, functional coatings, ecoecient car, plane & ships, improved tyres, recyclable materials. Technologies: Scale-up processes for the production of advanced materials, and process development and control technology. 5. Relevant initiatives During the last years several European Technology Platforms (ETPs) have been created and boosted by industrial and academic partners. A complete list of ETPs can be found at the website http://cordis.europa.eu/

European Construction Technology Platform (ECTP); www.ectp.org European Nanoelectronics Initiative Advisory Council (ENIAC); www.eniac.eu European Space Technology Platform (ESTP); http://estp.esa.int/exp/E10430.php Food for Life (Food); http://etp.ciaa.be/asp/ home/welcome.asp Future Manufacturing Technologies (MANUFUTURE); www.manufuture.org Future Textiles and Clothing (FTC); http://textile-platform.eu/textile-platform/ Nanotechnologies for Medical Applications (NanoMedicine); http://cordis.europa.eu/nanotechnology/ nanomedicine.htm Photonics21 (Photonics); www.photonics21.org Photovoltaics (Photovoltaics); www.eupvplatform.org

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Sustainable Chemistry (SusChem); www.suschem.org Water Supply and Sanitation Technology Platform (WSSTP); www.wsstp.eu/site/online/home For training and formation activities it is worth to mention the European School on Molecular Nanoscience that has been organized two editions in Spain with a successful attendance of young researchers from all Europe with the participation of worldwide recognized researchers and professors. This initiative was organized by the European Network of Excellence MAGMANet becoming an important international event where Nanochemistry plays a key role. There are also few Master Degrees that are given by some Spanish Universities where the training on chemistry and nanoscience is provided. 6. Infrastructure needed (2010-2013) Because of the special characteristics of Nanochemistry, there is no need to perform large investments in huge research facilities. The funds provided by the local and national governments must be addressed mostly to increase the manpower of the groups and to achieve ecient and rapid ways to acquire small-medium equipments without long waiting times since this decrease the eciency and competitiveness of the groups. 7. Conclusion As a general conclusion it is worth to mention the need to promote in Spain the research addressed to all the topics reported before. Nowadays there is a good level of research in our country in comparison with Europe although we are still far from the optimal rank of excellence and productivity existing in the most developed countries.
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In order to achieve such a level important nancial eorts must be made from the dierent national and local research agencies to provide with considerable amounts of funds to the most competitive Spanish laboratories and groups, judging their past activity based only in terms of excellence and productivity. The traditional attitude of such agencies to distribute small amounts of funds to all groups must be completely disregarded. Such agencies must also consider those small groups with promising backgrounds to boost their activities.

> FRANCESC PREZ-MURANO Place and date of birth Barcelona (Spain), 1966 Education PhD on Physics. Universitat Autonoma de Barcelona Experience Prof. Francesc Prez-Murano is research professor at IMB-CNM. His research activities are dedicated to developing novel methods of nanofabrication for micro and nano electronics, and to applications of MEMS and NEMS in the areas of Sensing. He made his PhD at the Universitat Autonoma de Barcelona, and he has made post-doctoral and visiting stays at MIC in Denmark, NIST in USA, AIST in Japan and EPFL in Switzerland. In 2001, he set-up the CSIC nanofabrication facilities and nanotechnology-oriented research at CNM-Barcelona. He has been strongly involved in EU collaborative research projects in FP5 and FP6 covering several aspects of Nanotechnology and Nanofabrication, including the coordination of an STREP project in FP6. He is co-author of more than 100 articles in peer reviewed International Journals and co-inventor of four patents. He is member of the Steering Committee of the MNE (Micro and Nano Engineering) conference series. francesc.perez@imb-cnm.csic.es
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1. Introduction It is widely accepted that electronics based on nano-scale integration and nanostructured molecular materials provides new types of devices and intelligent systems. Nanoelectronics technology development is following several approaches to improve performance of systems through miniaturization. On one side, electronics industry (traditionally called Microelectronics) relies on the classical top-down approach, where reliability and throughput is guaranteed to manufacture millions of chips with integrated nanoscale transistors. As stated by the well known Moores law, continuous reduction of the transistor size allows improving circuit performance. Microprocessors with 2 billion transistors (32 nm node) are now close to the market. The extremely complexity and cost of this technology, together with the envisioned limits for further miniaturization triggers the development of other concepts, materials and manufacturing technologies, encompassed in which are known as More than Moore and Beyond CMOS areas of nanoelectronics, according to ENIAC1 initiative. In this sense, the research area of nanoelectronics covers a large range of aspects, some of which will be revised in this report.

Figure 1. Dierent areas of Nanoelectronics according to the characteristic length of the devices.

Within the More than Moore area, microelectronics-based technology is used and extended to the fabrication of sensors and transducers, amongst other devices. A paradigmatic example of this is the growing area of nanoelectromechanical systems (NEMS). Beyond CMOS focuses on the introduction of disruptive, emerging materials and technologies aiming to continue the integrated circuits growing up device density race. Lot of development is being achieved in the so-called carbon-based electronics, where carbon nanotubes and graphene can be used to provide more-powerful devices. Along with this, polymers, single molecules and nanocrystals are also being introduced to developed new kind of concepts.

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The area of nanoelectronics and molecular electronics extends also towards materials science and chemistry on one side, and towards many aspects of sensing (including biosensing). These aspects are almost not treated in this report, which is mainly focused to information processing. At the end of the rst decade of the 21st century, we are in the situation where researchers and engineers are starting to take benet of the new nano-based materials and technologies originated in previous decades. We anticipate the outcome of a new area for nanoelectronics, where a real merge between top-down (microelectronics) and bottom-up (molecular electronics) will give place to extremely powerful systems to satisfy the increasing demands for ecient information processing and communications, including quantum computing. 2. State of the art 2.1 Miniaturization in Microelectronics Progress in nanotechnology and microelectronics is intimately linked to the existence of high quality methods for producing nanoscale patterns and objects at surfaces. The explosive growth in the capability of semiconductor devices has to a large extent been due to advances in lithography. Miniaturization has enabled both the number of transistors on a chip and the speed of the transistor to be increased by orders of magnitude. Optical lithography has kept pace with this evolution for several decades and has always been the workhorse for patterning the critical layers in semiconductor manufacturing. At present, technological solutions for the 32 nm node exist. Todays predominantly used technology, optical deep UV (DUV) lithography2 will be extended by computational methods to

further generations, however, 20 nm seems to be challenging. High volume, high throughput lithography is predicted to reach the sub 20 nm feature scale in 20173 . The technologies at hand to provide such a resolution at sucient feature quality are rare. Also, for the time being, it is not clear, if its potential successor, extreme ultraviolet (EUV) lithography is arriving at the market. Other technologies like nanoimprint lithography (NIL)4 or electron beam (EBL) maskless lithography5 provide sucient resolution. While EBL is too slow (and parallelization is dicult) to provide enough throughput for high volume production, NIL gathers increasing attention and it is proposed to be used in FLASH memory production in the near future6. However this solution still requires a mask technology with the added diculty to fabricate a 1X mask. In addition, because it is a contact lithography, mask defects is a main issue. Scanning Probe lithography for mask fabrication and technology development are being considered as well7. In any case, Microelectronics industry is seriously considering incorporating nanotechnology tools and concepts, like blockcopolymers self-assembly8. 2.2 Carbon based nanoelectronics (CNTs and Graphene) The approaching limits of the top-down miniaturization have triggered a global eort to generate alternative device technologies. By replacing the conducting channel of a MOS transistor by structured carbon nanomaterials such as carbon nanotubes or graphene layers, devices with enhanced properties for electronic transport are encountered9. Emerging of graphene as a high performance semiconductor material has been a major hit during 2007-2009. Key results on this aspects have been the achievement of ultrahigh electron mobility in

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2.3 Spintronics Spin based electronics deals with the manipulation of spin of charge carriers in solid state devices. It can be distinguished between inorganic spintronics (devices based on metals or semiconductors) and molecular spintronics, (either the design of molecular analogs of the inorganic spintronic structures and the evolution towards single molecule spintronics). A recent review about molecular spintronics can be found in15. Besides the well known impact of spintronics in storage technology (giant magneto-resistance eect used in the operation of magnetic hard-drives heads), inorganic spintronics has a potential to provide low-power devices for memories (MRAM). On the other hand, molecules and single-molecule magnets oer possibilities for future applications in quantum computing. 2.4 Nanoelectromechanical systems (NEMS) The area of nanomechanical systems has experienced a tremendous advance during the 2007-2009 period. Roughly, three main directions are being pursued: development of extremely sensitive nanomechanical sensors16, large scale integration of nanomechanical structures and quantum limits of nanomechanical resonators search. The area of

2.5 Molecular electronics Understanding the electronic properties of single molecules and developing methods for making reliable and optimal contacts to them are major challenges in Nanotechnology. Even though a single molecule electronic device is

Figure 2. Example of massive fabrication of nanoelectronics devices. A four inch-wafer containing 138,240 CNT-FET structures. I. Martin et al12.

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suspended graphene layers10 and the observation of room - temperature quantum hall eect. Technology for CNT-based nanoelectronic devices is arriving to a mature stage. Improvements on the control of CNT orientation and their combination with CMOS technology are especially relevant for future applications13. Also important are the new applications of CNT based devices for charge detection14 and for nanomechanical mass sensing (see below, NEMS subsection).

NEMS is a clear example of multidisciplinary eort, where the progress is achieved by simultaneous eorts on advanced nanofabrication processing, use of nanoscale characterization methods and tools, and introduction of concepts from photonics biochemistry physics, etc. NEMS technology include aspects of top-down fabrication using nanolithography and advanced optical lithography, but also combination with bottomup fabrication for the development of NEMS based on carbon nanotubes17 and silicon nanowires18. Most relevant results include the demonstration of single atom sensitivity for mass sensors using carbon nanotubes and silicon nanowires , the joint eort of CEA-LETI and UCLA to develop a robust/wafer scale technology for NEMS integration19, and the initial detection of the quantum limits of NEMS20 .

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conceptually simple (a molecule and two or three electrodes), it is not fully understood21. Some progress has been made to know the inuence of metal electrodes on the energy spectrum of the molecule, and how the electron transport of the molecules depend on the strengths of the electronic coupling between the molecule and the electrodes. A major drawback is the lack of reproducible results from single molecule devices due to the lack of control of the electrode/molecule contact, since most results are based on mechanical methods. Alternatives to develop functional integrated systems based on organic molecules are the ones related with the cross-bar structure22, a periodic array of crossed nanowires with a monolayer of an organic material (for example, bi-stable [2] rotaxane molecules) in between. It is proved that these systems can be miniaturized further than CMOS technology and that it is highly tolerant to manufacturing defects23. 3. Survey of relevant publications by Spanish and International groups in the area (2007-2009) 3.1 Spanish groups Spanish research community is very active in the area and some groups are in the cutting edge of the research arena. The present survey is not exhaustive and it is just intended to show the high-quality research performed by Spanish groups. Miniaturization in Microelectronics J. Martnez, R. V. Martnez, R. Garca. Silicon Nanowire Transistors with a Channel Width of 4 nm fabricated by Atomic Force Microscope Nanolithography. Nano Letters 2008 8 (11), 3636-3639. I. Martn. Sansa, M.J. Esplandiu, E. LoraTamayo, F. Prez-Murano, P. Godignon. Massive manufacture and characterization of single-walled carbon nanotube field effect transistors. Microelectronics Engineering, in press. (2010).

Carbon based nanoelectronics (CNTs and Graphene) A. Barreiro, M. Lazzeri, J. Moser, F. Mauri, A. Bachtold. Transport properties of graphene in the highcurrent limit. Phys. Rev. Lett., 103, 076601 (2009). A. Gruneis, M. J. Esplandiu, D. Garca-Sanchez, and A. Bachtold. Detecting Individual Electrons Using a Carbon Nanotube Field-Effect Transistor. Nano Lett., 7, 3766 (2007). Per Sundqvist, Francisco J. Garca-Vidal, Fernando Flores, Miriam Moreno-Moreno, Cristina Gmez-Navarro, Joseph Scott Bunch, and Julio Gmez-Herrero. Voltage and Length-Dependent Phase Diagram of the Electronic Transport in Carbon Nanotubes. Nano Letters 2007 7 (9), 25682573. H. Santos, L. Chico, L. Brey. Carbon Nanoelectronics: Unzipping Tubes into Graphene Ribbons. Physical Review Letters, 103, 086801 (2009). Spintronics M. Reyes Calvo, Joaqun Fernndez-Rossier, Juan Jos Palacios, David Jacob, Douglas Natelson & Carlos Untiedt. The Kondo effect in ferromagnetic atomic contacts. Nature 458, 1150-1153 (2009). Eugenio Coronado, Arthur J. Epsetin, Editors. Molecular Spintronics and Quantum Computing. Special Issue of Journal of Materials Chemistry, vol 19, 1661-1760 (2009). J. Fernndez-Rossier and J. J. Palacios. Magnetism in Graphene Nanoislands. Phys. Rev. Lett. 99, 177204 (2007). V. A. Dediu, L. E. Hueso, I. Bergenti and C. Taliani. Spin Routes in Organic Semiconductors. Nature Materials 8, 707 (2009).

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L.E. Hueso, J.M. Pruneda et al. Transformation of spin information into large electrical signals using carbon nanotubes. Nature 445, 410 (2007). NEMS B. Lassagne, D. Garcia-Sanchez, A. Aguasca, and A. Bachtold. Ultrasensitive Mass Sensing with a Nanotube Electromechanical Resonator. Nano Lett. 8, 3735 (2008). J. Mertens. C. Rogero, M. Calleja, D. Ramos, J.A. Martn-Gago, C. Briones, & J. Tamayo. Label-free detection of DNA hybridization based on hydration-induced tension in nucleic acid films. Nature Nanotechnology 3 (5) (2008). J. Arcamone, M. Sansa, J. Verd, A. Uranga, G. Abadal, N. Barniol, M. van den Boogaart, J. Brugger, F. Prez-Murano. Nanomechanical mass sensor for spatiallyresolved ultra-sensitive monitoring of deposition rates in stencil lithography. Small, 5, 176-180 (2009). lvaro San Paulo, Noel Arellano, Jose A. Plaza, Rongrui He, Carlo Carraro, Roya Maboudian, Roger T. Howe, Jeff Boko, and, Peidong Yang. Suspended Mechanical Structures Based on Elastic Silicon Nanowire Arrays. Nano Letters 2007 7 (4), 1100-1104. Molecular Electronics J. Hihath, C. R. Arroyo, G. Rubio-Bollinger, N. J. Tao, N. Agrat. Study of Electron-Phonon Interactions in a Single Molecule Covalently Connected to Two Electrodes. Nanoletters 8, 1673-1678 (2008). M del Valle, R. Gutirrez, C. Tejedor and G. Cuniberti.
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J Puigmart, V. Laukhin, A.P. del Pino et al. Supramolecular conducting nanowires from organogels. Angewandte Chemie International Edition 46238-241 (2007). 3.2 International groups Miniaturization in Microelectronics A. Pantazi et al. Probe-based ultrahigh-density storage technology. IBM J. Res. Dev. 52, 493511 (2008). C.T. Black et al. Polymer self-assembly in semiconductor microelectronics. IBM J. Res. & Dev. 51, 605 (2007). Carbon based nanoelectronics (CNTs and Graphene) KI Bolotin, KJ Sikes, Z Jiang, M Klima et al. Ultrahigh electron mobility in suspended graphene. Solid State Communication 146, 351 (2008). KS. Novoselov, Z Jiang, Y Zhang, SV Morozov, et al. Room-temperature quantum Hall effect in graphene. Science 315, 652 (2007). Nanoelectromechanical systems (NEMS) A. K. Naik, M. S. Hanay, W. K. Hiebert, X. L. Feng, M. L. Roukes. Towards single-molecule nanomechanical mass spectrometry. Nature Nanotechnology 4, 445 (2009). K. Jensen, K Kim, A Zettl. An atomic-resolution nanomechanical mass sensor.

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H. Lpez, X. Oriols, J. Su, X. Cartoixa. High-frequency behaviour of the Datta-Das spin transistor. Applied Physics Letters 83, 193592 (2008).

Tuning the conductance of a molecular switch Nature Nanotechnology 2, 176 (2007).

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Nat. Nanotech. 3, 533, 2008. J. D. Teufel, T. Donner, M. A. CastellanosBeltran, J. W. Harlow and K. W. Lehnert, Nanomechanical motion measured with an imprecision below that at the standard quantum limit. Nature Nanotechnology 4, 820 (2009). Molecular Electronics K. Moth-Poulsen and T. Bjornholm. Molecular electronics with single molecules in solid-state devices. Nature Nanotechnology 4, 551 (2009). J. E. Green, J. W. Choi, A. Boukai, Y Bunimovich et al. A 160-kilobit molecular electronic memory patterned at 1011 bits per square centimetre Nature 445, 414 (2007). W. Lu and C. Lieber. Nanoelectronics from the bottom up. Nature Materials 6, 841 (2007). 4. Actions to develop in Spain for the period (2010- 2013) Future impact in the society of nanoelectronics and molecular electronics will be dictated by the envisioned end of the miniaturization of CMOS microelectronics technology, which will open enormous opportunities to the new building blocks from Nanotechnology. It is now time to position in this aspect. Nanoelectronics and molecular electronics community in Spain, although demonstrating a high quality research activity, it looks quite fragmentized in small groups dealing with partial aspects of the eld. As the future of the area relies on a multidisciplinary approach, some actions that could be undertaken to assure a competitive position of Spain in this area are: Enhance the relation between the different groups active on nano-electronics and

molecular electronics. Large joint projects in the area, creation of networks, workshops, etc., should be proposed. Increase the critical mass of research groups active in the area. Analyze/unify the undergraduate and postgraduate education in the area, enhancing the programs content. 5. Research infrastructure required Technological development for nanoelectronics and molecular electronics requires the use of clean room facilities and equipment. There is an increasing number of small size clean rooms in Spain that could provide an adequate environment for activities focused to basic/fundamental science. In addition, granted access to medium-size clean rooms (CNM clean room, ISOM clean room) is available to Spanish researchers through dedicated programs nanced by the Ministry of science and Innovation (MICINN). However, more ambitious technological developments that would provide integrated solutions based on nano-electronics and molecular electronics requires updating and extending present capabilities, since, as previously stated, multidisciplinary approach is required for future developments of nanoelectronics. Additionally well trained sta enhancing the managing and operating capabilities of the above mentioned free access facilities need to be boosted. In this sense, actuations related with infrastructure should be focused to consolidate small-size clean room focused to basic research application and enforce medium-to-large size clean rooms that would allow them to adequately address challenges for technological developments in nanoelectronics. Adequate programs for funding and training dedicated technical sta related with the clean rooms are clearly required.

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ENIAC is the well known European technological platform in the area of nanoelectronics (www.eniac.eu). Its main goal was to dene common research and innovation priorities to ensure a truly competitive nanoelectronics industry in Europe. Recently, the rst research projects funded by ENIAC have started. The research is largely focused to industrial application, with emphasis in More Moore and More than Moore areas. ICT program of FP7 (http://cordis.europa.eu/ fp7/ict/) funds more exploratory projects related with nanoelectronics, including aspects of More than Moore and Beyond CMOS areas. Within ICT, The Future and Emerging Technologies Open Scheme - FET-Open - is a roots-up approach for exploring promising visionary ideas that can contribute to challenges of long term importance for Europe. The scheme stimulates nonconventional targeted exploratory research cutting across all disciplines, and acts as a harbour for exploring and nurturing new research trends, helping them mature in emerging research communities. Nano-ICT (www.phantomsnet.net/nanoICT) is a VII FP coordination action whose main objective is the consolidation and visibility of the research community in ICT nanoscale devices. Nano-ICT is structured in several working groups including Alternative Electronics, NEMS, Carbon nanotubes, spintronics and mono-molecular electronics. Within the Marie Curie training networks, for example FUNMOLS (fundamentals of molecular electronic assemblies) has Spanish participation. At the national level, several projects within nanoelectronics are funded within the Plan Nacional at dierent programs: TEC (Electronics and Communication Technologies), MAT (Materials) and FIS (Physics), and also within the Consolider-Ingenio initiative (as for exemple
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Courses at post-graduate level including subjects related with nanoelectronics and molecular electronics are available at most of Science and Technical Universities around Spain. 7. Conclusions The expected end in few years of the miniaturization trend in microelectronics as we know it today, places nanoelectronics and molecular electronics as critical actors to provide future advances for the areas of information processing and storage. In Spain there is an ongoing important and high quality research activity in this area, with already good expertise. However the area looks fragmentized in the sense that there is no coordination between the groups and activities, which would allow to better use resources and expertise, and then position Spain in a compettive place in the international arena. Acknowledgments The author acknowledge helpful discussions with Adrian Bachtold, Nuria Barniol, Carles Can, Xavier Cartoixa, Jordi Fraxedas, Ricardo Garcia, and Emilio Lora-Tamayo. References
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www.eniac.eu M. Rothschild, Materials Today, 8, 18 (2005).

International Technology Roadmap for Semiconductors (ITRS), Semiconductor Industry Association, (2008).

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6. Relevant initiatives

Nanoselect, Nanobiomed and Nanociencia Molecular). Relevant networks nanced including topics of interest for nanoelectronics are Nanospain and Nanolito.

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H. Schift, J. Vac. Sci. Technol. B, 26, 458 (2008).

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K. Jensen et al, Nat. Nanotech. 3, p533 (2008). R. He et al, Nano. Lett. 8, p1756 (2008).

R. Menon, A. Patel, D. Gil, H. I. Smith, Material Today, 8, 26 (2005).

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M. LaPedus, "Toshiba claims to 'validate' nanoimprint litho," EETimes, October 16, 2007.
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A. Pantazi et al. Probe-based ultrahigh-density storage technology. IBM J. Res. Dev. 52, 493511 (2008).

P. Andreucci, Very Large Scale Integration (VLSI) of NEMS based on top down approaches. Minatec Cross Road Workshop Nanomechanics for NEMS : scientic and technological issues. Minatec Grenoble (2008).
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C.T. Black et al. Polymer self-assembly in semiconductor microelectronics. IBM J. Res. & Dev. 51, 605 (2007).
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J. D. Teufel, T. Donner, M. A. CastellanosBeltran, J. W. Harlow and K. W. Lehnert, Nanomechanical motion measured with an imprecision below that at the standard quantum limit. Nature Nanotechnology 4, 820 (2009).

Ph. Avouris, Z. Chen and V. Perebeinos. Nature nanotechnology, 2, 605 (2007).

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K. Moth-Poulsen and T. Bjornholm. Nature Nanotechnology 4, 551 (2009). Jonathan E. Green et al. Nature 445, 414 (2007); W. Lu and C. Lieber. Nature Nanotechnology 6, 841 (2007).
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KI Bolotin et al. Solid State Communication 146, 351 (2008). KS. Novoselov et al. Science 315, 652 (2007).

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J. Heath et al. Science 280, 1716 (1998).

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I. Martn, M. Sansa, M.J. Esplandiu, E. LoraTamayo, F. Perez-Murano, P. Godignon. Massive manufacture and characterization of singlewalled carbon nanotube eld eect transistors. Microelectronics Engineering (2010). SJ Kang et al, Nature Nanotechnology 2, 230 (2007). A. Gruneis, M. J. Esplandiu, D. Garca-Snchez, and A. Bachtold Nano Lett., 7, 3766 (2007).

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Eugenio Coronado, Arthur J. Epsetin, Editors. Special issue of Journal of Materials Chemistry, vol 19, 1661-1760 (2007).

A. K. Naik, M. S. Hanay, W. K. Hiebert, X. L. Feng, M. L. Roukes Towards single-molecule nanomechanical mass spectrometry.Nature Nanotechnology 4, 445-450 (2009).

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> RODOLFO MIRANDA Place and date of birth Almera (Spain), 1953 Education 1975 BS in Physics, Universidad Autnoma de Madrid (UAM). Madrid, Spain; 1981 PhD with Prof. Juan M. Rojo, UAM, Madrid, Spain; 18821984 Postdoc with Prof. G. Ertl, Physikalische Chemie Institut de la Universidad de Munich, Munich, Germany. Experience Full Professor of Condensed Matter Physics of the Faculty of Sciences at the UAM, Madrid, Spain & Director of the Madrid Institute for Advanced Studies in Nanoscience (IMDEA-Nanociencia). Prof. Miranda has been Vice-chancellor of Research and Scientic Policy (1998-2002) at the Universidad Autnoma de Madrid, Executive Secretary of the R&D Commission for the Conference of Rectors of Spanish Universities (CRUE) (2000-2002) and Director of the Materials Science Institute Nicols Cabrera at the Universidad Autnoma de Madrid. Prof. Miranda is Fellow of the American Physical Society (2008) and Member of the following societies: American Vacuum Society, American Physical Society, and Materials Research Society. Other honours include Membership of the Surface Science Division Committee IUVSTA (October 1989- October 1992), of the Advisory Board at the Max Planck Institute fr Mikrostrur Physik, Halle (1993-2003), and the Spanish representative in the Scientic Advisory Committee of the European Synchrotron Radiation Facility (ESRF) at Grenoble (July 1988-January 1991). He is also a member of the Editorial Board of the journal Probe Microscopy. Prof. Miranda has published more than 200 scientic articles. rodolfo.miranda@imdea.org > ROBERTO OTERO Place and date of birth Crdoba (Spain), 1974 Education Degree in Physics at UAM (1997) and PhD in Science at UAM (2002) Experience Three years as Assistant Research Professor at the University of Aarhus and four years as Ramn & Cajal at UAM. roberto.otero@imdea.org

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1. Introduction A great deal of the expectations raised in the last decade in the elds of Science and Technology at the atomic scale arise from the lack of scalability in the physical properties of matter when its size falls in the nanometer range (the millionth part of a millimeter). Nanoscopic pieces of material can be made out of hundreds of atoms (at least in the dimension in which the size of the material is in the nanometer range) instead of the mind-boggling amount of 1023, characteristic of macroscopic materials. It is thus not surprising that many of the commonly used approximations to understand the physical properties of large-scale materials cannot be applied to nanometer-scale structures. Among these properties we nd for example electrical conductivity, that becomes quantized in the limit of nanometer-thick wires; the chemical reactivity of nanoparticles, which is dramatically aected by the larger number of surface atoms in these nanostructures as compared to macroscopic materials; the magnetization of nanoscale magnets, that can be severely reduced by the non-negligible eect of thermal uctuations, etc. These eects exemplify that fact that the physical properties of nanostructures can therefore not be obtained simply by scaling-

down the physical properties of macroscopic pieces of the same material. The lack of scalability in the physical properties of nanometer-sized structures opens new opportunities and methods for the fabrication of nanoscopic structures with custom-desgined physical properties and, therefore, for the Science of Materials hosting nanometer-scale structural motifs. In the following we will focus on recently developed methods to provide macroscopic materials with nanometer-scale structural motifs able to modify their physical and chemical properties and endorse them with new functionalities. We will however not discuss the synthesis and properties of individual nanostructures, which also a burgeoning eld with great potential for applications, but which will most likely be covered in other sections of this report. We will however make an exception for the explosive development of the research in graphene, i.e. an atom-thick graphite layer. The discovery of methods to isolate and handle individual graphene sheets has raised many expectations in the eld of Nanoelectronics, due to its promising transport properties, which ultimately arise from a peculiar electronic band structure leading to very high Fermi velocity (of the order of 106 m/s), giant electronic mobility (in excess of 104 cm2/Vs) and zero eective

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mass. From the point of view of Materials Science, the most important challenges to meet are the chemical functionalization of graphene (to control its solubility, open a semiconducting gap and control the sign and concentration of charge carriers by doping) and the epitaxial growth of graphene sheets with reduced defect concentration. An analysis of the scientic papers published in the eld of graphene research in the last few years (2007-2009), shows that Spain has played a major role in this scientic enterprise, occupying the 7th position in the ranking of countries, according to Web of Science. 2. State of the Art As described above, we will limit ourselves to the Materials Science aspects of current Nanoscience and Nanotechnology, i.e. to materials that contain distributions of nanoscale motifs that control or aect their macroscopic properties. Since their preparation methods and nal properties are very dierent, we will classify nanostructured materials depending on whether the nanoscale motifs are distributed all over the bulk of the material or at its surface. 2.1 Embedding nanostructures at the bulk of a material Nanostructures can be embedded in typically amorphous matrices, very often polymeric matrices, resulting usually in random spatial distribution and the nanoscale structural motifs. Typical examples are polymeric matrices with incorporated carbon nanotubes, which have very interesting eects in their elastic and thermal conduction properties, or semiconducting nanoparticles (quantum dots) dispersed in polymeric matrices with very interesting photovoltaic properties. Recently, hybrid CNT-QD systems have been synthesized, holding promise for photovoltaic

applications. A very intense research eort is currently being developed to solve nanostructures in the bulk of liquids. Solubilization and biocompatibilization of light emitting and magnetic nanoparticles are currently a hot topic for nanomedicine studies. New experimental non-invasive imaging techniques and therapies for a number of diseases, which are currently being developed, relay on the capability of these nanostructures to get incorporated into the blood stream without triggering immune responses, and get into target cells and organs. For this purpose a major challenge that must be tackled in the next few years is nding the proper chemical functionalizations that would enable the nanostructures to bind selectively to the targeted organs. One possible alternative to incorporate the nanostructures into a bulk material without the need of a matrix could be the direct crystallization of nanoparticles. The interactions between the nanoparticles that steer the selfassembly processes are dictated, and thus can be controlled, by the proper choice of the ligands that cover their surfaces. It was already described in the literature that nanoparticles can be embedded into larger colloidal particles, for which crystallization methods have been long known. The resulting photonic crystals have very interesting optical properties. Nanoporous materials, such as zeolites or organometallic coordination networks, can act as molecular sieves with very promising applications in the elds of catalysis and water purication. The directionality of the bonds that hold the 3D structure of these materials, leads to the formation of ordered arrays of holes with well

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dened size, shape and chemical composition. These pores can selectively bond molecules with particular shapes, enabling their function as catalysts and molecular sieves. 2.2 Surface Nanostructuration of Materials The surfaces of materials can be modied at the nanometer scale either by imprinting nanoscale patterns on the otherwise homogenous surface, or adsorbing nanostructures on them, which could be either preformed and then deposited or can be self-assembled from their constituent building blocks previously adsorbed on the surface. Both approaches can be combined by adsorbing nanostructures selectively on particular areas of a imprinted nanoscale pattern. In this way, for example, linear nanopatterns can be used to direct the growth of 1D arrays of nanoparticles, something that would be very challenging to do only by exploiting self-assembly processes.

However, the time-honored, most commons lithographic techniques are based on irradiating the surface of the material (previously covered by a radiation-sensitive layer) with energetic particles (photons, electrons, ions) through some masks with orices of well dened shape and size. The smallest nanostructures achieved hitherto by electron beam lithography are some in excess of 10 nm large. In order to achieve even smaller nanostructures, the possibility of performing lithography with the tip of a Scanning Probe Microscope is currently under investigation. Such method, though, still has to face the problem of scaling up the modied area, since today only relatively small patches of the surface can be modied within a reasonable time-span. There are also non-lithographic methods to imprint nanoscale patterns on solid surfaces. They are usually based on obtaining an ordered array of nanostructures in the surface by epitaxy or self-assembly. This array will act as a nanoscale pattern for the subsequent adsorption of other kind of nanostructures. For example, epitaxial growth of graphene on transition metal surfaces leads to nanoscale Moir patterns originating from the lattice mismatch between the underlying metallic surface and the graphene layer. This Moir pattern has been shown to direct the growth of metallic nanoparticles or organic material deposited on the rippled graphene. Nanoscale patterns can also be obtained from

Figure 1. Hybrid carbon nanotube Quantum Dot system. From Nano Lett. 7, 3564 (2007). Courtesy of B. H. Jurez

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The methods to imprint patterns on surfaces are collectively termed lithographies. The simplest of them is the microcontact printing technique, in which a stamp is dipped into an ink (a solution of molecules or nanostructures) and then brought into contact with a surface, so that the ink wets the surface preferentially following the pattern at the stamp.

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the self-assembly or organic molecules by hydrogen bonds or coordination bonds, and the pores of the molecular network act as nucleation sites for the subsequent deposition of organic material. Finally, nanoparticles or nanowires can also be directly deposited on solid surfaces. Hitherto most of these works have performed the deposition directly from a solution of the nanostructures, by drop-casting, spin-coating or Langmuir-Blodgetts techniques. In the last few years several groups have pursued new methods to deposit these nanoparticles under vacuum conditions, with methods based on electrospray evaporation, laser irradiation sublimation (MALDI) or pulsed-valve methods. Functionalizing solid surfaces with nanoparticles is known to have some very interesting eects on the material reactivity or photovoltaic properties. Controlling the self-assembly of nanoparticles on solid surfaces remains however a challenge in which more work needs to be developed in forthcoming years. The adsorption of molecular wires such as DNA and carbon nanotubes faces similar problems nowadays. In this respect, however some interesting progress has been made by deposition of the catalytic promoters on nanopatterned surfaces, which direct the growth of the CNT is specic directions. 3. Relevant publications 20072009 Novoselov K. S. et al. Room-temperature quantum hall effect in graphene, Science 315, 1379 (2007). Sutter P. W., Flege J. I. & Sutter E.A. Epitaxial graphene on ruthenium, Nat. Mater.7, 406 (2008). Wehling T. O. et al. Molecular doping of graphene, Nano Lett. 8, 173 (2008). Gmez-Navarro C. et al. Electronic transport
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properties of individual chemically reduced graphene oxide sheets, Nano Lett. 7, 3499 (2007). Elas D. C. et al. Control of Graphene's Properties by Reversible Hydrogenation: Evidence for Graphane, Science 323, 610 (2009). Vzquez de Parga A. L. et al., Periodically rippled graphene: Growth and spatially resolved electronic structure. Phys. Rev. Lett. 100, 056807 (2008). Brown, P. & Kamat, P. V, Quantum Dot Solar Cells. Electrophoretic Deposition of CdSeC60 Composite Films and Capture of Photogenerated Electrons with nC60 Cluster Shell, J. Am. Chem. Soc. 130, 8890 (2008). Zheng, D. et al. Aptamer Nano-flares for Molecular Detection in Living Cells, Nano Lett. 9, 3258 (2009). Striemer, C. C. et al. Charge- and size-based separation of macromolecules using ultrathin silicon membranes Nature 445, 749 (2007). Kang, H. et al. Hierarchical Assembly of Nanoparticle Superstructures from Block Copolymer-Nanoparticle Composites Phys. Rev. Lett. 100, 148303 (2008). Green, J. E. et al. A 160-kilobit molecular electronic memory patterned at 1011 bits per square centimeter Nature 445, 414 (2007). Guo, L. J. Nanoimprint Lithography: Methods and Material Requirements Adv. Mater. 19, 495 (2007). Park, S. Y. et al. DNA-programmable nanoparticle crystallization, Nature 451, 553 (2008). Jurez, B. H. et al. Quantum Dot Attachment and Morphology Control by Carbon Nanotubes, Nano Lett. 7, 3564 (2007). cija, D. et al. Crossover Site-Selectivity in the Adsorption of the Fullerene Derivative PCBM on Au(111) Angew. Chem. Intl. Ed. 46, 7874 (2007).

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4. Actions to develop in Spain 20102013 It was mentioned above that the state of scientic research in some areas of nanomaterials science is quite competitive worldwide. However, if we expand our publication research (based on Web of Science data) to the larger eld of nanomaterials in general, we nd the Spain is only the 14th in rank of publishing countries. This fact shows that Spain has nowadays the manpower required to take the lead in the pursuit of some of the hottest topics in nanomaterials science research, but it nonetheless lacks enough scientic infrastructures, evaluation mechanisms and educational opportunities to exploit at full its human potential. The actions to be undertaken in the near future must aim at the double objective of keeping and reinforcing our leadership in those successful areas, such as graphene research, Scanning Probe Microcopies of Nanobiotechnology, while promoting high-quality scientic research in those areas in which it is missing and yet they are recognized as strategically relevant for our country. In the following we enumerate a number of suggested actions that could help us getting closer to our objectives: In the last few years, a number of research centers with specific focus on nanoscience and nanotechnology have appeared in different regions of Spain. These centers should keep a sufficient funding to become attractive to foreign researchers or Spanish researchers working abroad. In order to keep the level of scientific funding high in the midst of an economic crisis, it is important that serious evaluations of research outcomes are routinely done, and that the results of such evaluations is taken into account to obtain further funding. Nanoscience is an interdisciplinary research

Strategic research objectives should be clearly defined, and sufficient funding should be delivered as Strategic Actions into particular fields both to keep the leadership in successful areas and promote new topics in the Spanish scientific landscape. In general a closer contact between scientific research and industry must be pursued. 5. Required infrastructure The founding over the last few years of a number of research centers with a focus on nanoscience research can in principle provide the Spanish scientic community with a strong structural basis to pursue scientic excellence and leadership worldwide. In the next few years they should be equipped with the scientic infrastructure and technology that will enable them to develop high-quality scientic research. The required investment must be evaluated by external scientic committees to ensure that the funds are really helping capable researchers to carry out relevant investigations. Constant and uid communication channels must be open among research groups and among nanoscience centers. Thus, the creation of new scientic and technological networks and the promotion of the already existing ones, such as the successful NanoSpain network must be one of the axes of scientic policy.
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field in its very essence. Promoting interdisciplinarity is thus an important requirement for leadership in nanoscience research. Some actions that would help promoting interdisciplinarity are the following: positive evaluation of interdisciplinary curricula in calls for public funding; promotion of interdisciplinary research centers, such as the new nanoscience centers; promotion of postgraduate master courses, perhaps by merging some of the very specific courses nowadays available in Spanish universities into larger ones with broader scopes.

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Spanish scientic community will prot extraordinarily from the availability of large infrastructures, such as synchrotron radiation sources, in Spain. The existence and use of these facilities must be promoted by sucient funding and quality sta, so that they can become competitive with similar European facilities, with which Spanish researchers are already familiar and, in many cases experienced users. 6. Relevant initiatives Spanish scientists in the Nanostructured Materials research eld can prot from several Spanish and European initiatives aimed at several ends of networking, educational opportunities, fundraising, etc. Some of these opportunities are listed below: NanoSpain network (www.nanospain.org): This network brings together almost every research group in the areas of Nanoscience and Nanotechnology in Spain promoting communication and networking in different ways such as an annual conference. Master in Molecular Nanoscience (www.icmol.es/master/nnm/index.php): Postgraduate courses in Nanoscience in which different Universities are involved. It provides students with a general interdisciplinary view of the different fields contributing to Nanoscience. Many Universities in Spain offer postgraduate courses in particular aspects of Nanoscience and Nanotechnology. 7. Conclusions The discovery of new and promising properties of nanostructures are revolutionizing the eld of Materials Science. It is impossible today to imagine a future for Materials Science without including concepts, methods and materials taken from the eld of Nanoscience.
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Several aspects of nanostructured materials seem particularly relevant today, such as for example carbon-based electronics, specially based on graphene and carbon nanotubes; the use of nanoparticles in biomedicine; the magnetic properties of nanostructured materials or the use of self-assembly processes to direct the growth of nanostructures. Spain is performing well in some of these elds, although works still remains to be done in other elds to achieve the level of scientic excellence in the international arena. An adequate level of funding, evaluation of scientic results and the promotion of the new Nanoscience centers seem to be the cornerstones of any scientic policy aimed at helping the progress of Materials Nanoscience in our country.

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N A N O M E T R O L O G Y, N A N O - E C O - T O X I C O L O G Y A N D S TA N D A R D I Z AT I O N

> XAVIER OBRADORS Place and date of birth Manresa (Spain), 1956 Education Degree in Physics, Universitat de Barcelona , June 1978. DEA in Physique des Solides, Universit de Toulouse, June 1980. Ph.D. in Physics, Universitat de Barcelona , October 1982. Doctorat Materials Science , Universit Scientique et Mdicale de Grenoble , January 1983. Research and teaching positions Assistant Professor, Universitat de Barcelona, June 1978-79. Doctoral fellow, CNRS Toulouse and Grenoble, 1979-82. Postdoctoral fellow and Assistant Professor, Universitat de Barcelona, 1982-85. Professor, Universitat de Barcelona, 1985-89. Research scientist (1989-92) and Research Professor (1992-), National High Research Council. Head of the Dpt. of Magnetic and Superconducting Materials, 1991-2002. Vice-Director (2002-2008) and Director (2008-) Materials Science Institute of Barcelona, CSIC. Research interests and strategy The research activity promoted within the Magnetic and Superconducting Materials Department at ICMAB-CSIC has always been marked by a very broad approach, including materials preparation with controlled microstructures and the search for the comprehension of the physical mechanisms underlaying the magnetic and superconducting properties of the materials. The generation of industrially signicant knowledge, both in materials processing and in electrotechnical device development, has been strongly stimulated. Several initiatives of technological transfer within an European scenario have been carried out. xavier.obradors@icmab.es
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1. Introduction The energy challenge of Humankind has become one of the greatest social, environmental, economical and technological (and hence scientic) priorities since the recognition that global warming cant be ignored any more. Achieving a reliable and sustainable energy supply and use is an issue of the highest relevance in order to avoid an undesirable climate change with potential devastating power. At present the worldwide use of energy of fossil origin is around 80 % while it is estimated that to stabilize the CO2 content in the atmosphere at about 450-500 ppm (to limit the mean temperature increase of the earth to less than 2-3OC) would require at least achieving 50 % of clean energy (carbon-free), even including the expected population rise (from ~6x109 to ~10x109 inhabitants by 2050) and the corresponding consumption increase per capita (mainly of the developing countries). This vision is extremely challenging and therefore intermediate objectives in terms of reduction of green house gas (GHG) emissions are being established. Europe, for instance intends to achieve by 2020 the target of cutting 20 % GHG emissions, increase the share of renewable generation to 20 % and reducing 20 % the use of primary energy through enhanced eciency. The energy policies being considered
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worldwide can only be successful through a decisive increase of the R&D on energy technologies where many breakthroughs are needed to fulll the performances and costs required for a really successful low-carbon economy. It is undoubtful that there is ample room for eciency improvement on conventional fossil-related energy technologies or nuclear energy and certainly new scientic developments are capable of improving incrementally its eciency. This type of activities will not be covered by the present report. Instead, advanced technologies having a strong potential to reduce GHG emissions and with a long way to go in terms of technological development will be the main choice. Nanoscience and nanotechnology, and the corresponding materials technologies derived from them, are crucial to achieve the ambitious goals established to create a myriad of new sustainable technologies. Actually, sustainable technologies are still on its infancy and they are very far from their fundamental limits. At the same time, we must be aware that the energy industry is essentially driven by cost and so no signicant change in the energy mix will occur unless low cost is achieved in parallel to the enhanced performances based on varied functionalities. It is a big priority to break this bottleneck to achieve a wide spread of renewable energy sources and an ecient use of energy.

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Many dierent areas have a huge potential to contribute to the energy challenge of 21st century, as it will be described later. However, it is clear that the requirements of the new nanomaterials to be used for energy purposes is that they can be produced at large scale and at low cost. Therefore the bottom-up approach to nanofabrication will be the preferred choice in the long term, even if this may induce some reduction of performances. Top-down approaches to nanomaterials fabrication can be however considered as very appealing for proof -of-principle new technology demonstration or also as elements for devices of intermediate cost but with very high performances. While the nanofabrication issues considered for energy uses are quite unique and require a widespread development of new methodologies, the demands in terms of nanoscale characterization are also very demanding because the advanced functionalities are associated in most of the cases to interfaces of materials with varied shapes and forms. It is particularly outstanding the need of chemical composition and structural characterization tools at the nanoscale such as electron nanoscopy. 2. Worldwide state of the art Energy harvesting, transport, storage and use can be performed in many ways and under many circumstances or for dierent purposes (transport, domestic, industry) therefore it is a dicult task to shortly summarize the R&D advances and the bottlenecks. Even though, a classication of the worldwide activities following the general energy forms has the advantage of some thematic similarity, even if an intermixing of all them can actually not be avoided. Three wide conceptual groups have therefore been selected which cover the two more promising sustainable vectors, i.e.
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electricity and hydrogen: chemical energy, electronic energy and electric energy. 2.1 Chemical energy The most promising alternative to fossil fuels, particularly for transport purposes, is hydrogen, an energy carrier which is abundant in chemical compounds such as water and biomass. When used as vector of the hydrogen-water cycle it becomes a sustainable choice if it uses renewable resources for generation. The whole cycle involves therefore generation, storage and nal use, for instance with fuel cells. In all the three stages nanotechnology is required to achieve a mature and ecient hydrogen energy chain. Hydrogen production with low CO2 generation can arise from biomass or by photocatalytic splitting of water. Both strategies require specic nanostructured materials, either for catalytic purposes or as semiconductors harvesting light to split water. Noble metals supported on oxide nanoparticles continue to be the preferred choice in these catalytic processes and much more knowledge is being generated about the active sites and mechanisms through the structural and spectroscopic analysis of surfaces oxides under real working conditions. Oxide, oxynitride and sulde nanoparticles and nanorods, together with semiconducting nanowires, are being very actively investigated as photocathodes for electrochemical cells performing water splitting from the visible light spectra. The tuning capability of the quantum yield has shown a steady progress based on further understanding of the physical and chemical processes involved. The practical application of this technology requires an important increase of eciency which must be linked to new materials discovery, as well as a tight control of nanostructure of the photocatalysts and the semiconductors.

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2.2 Electronic energy Electronic materials are mainly semiconductors which can easily convert light or heat on electrons and viceversa and are therefore essential for energy purposes. It is particularly worthwhile to stress the most promising opportunities in photovoltaic generation converting visible and UV photons (58 % of solar spectrum) on electrons and thermoelectric materials for electron generation from infrared radiation (42 % of the solar energy spectrum). Within this same classication we can include lightening materials such as LEDS. Photovoltaic cells are usually classied as 1st generation (Si based), 2nd generation (thin lms such as chalchogenides CIGS and organic or hybrid cells) and 3rd generation (multijunction and nanodot assisted semiconductor cells). The three categories are characterized in terms of achievable eciency and cost per useful power. While 1G cells can be fabricated with 20-25% eciency (very near the thermodynamic limit of 31%) but in limited surfaces, 2G cells concentrate on potentially large area materials with reduced cost (organic and hybrid cells and thin lms), at cost of reducing eciency (8-10% at most at present). 3G cells are based on multilayered semiconductors including nanodots where eciency can be very high (near 60%), even if they are fabricated at a higher cost. The organic cells might to be used on very wide areas, for instance as indirect light recycling devices, while the 3G cells are at the core of solar concentration systems.

Fuel cells using hydrogen to generate eciently electricity with water as exhaust are an environmentally friendly alternative with a high eciency and versatility. Polymer electrode membranes and solid oxide fuel cells (SOFC) are two alternative technologies working at dierent temperatures which are continuously displaying a progress in performance, life time and cost reduction. One particular concern is to substitute expensive catalysts such as Pt. Understanding the interplay between nanostructure, composition and the performances of electrolyte and electrodes (ionic conduction, electronic conduction, catalytic activity) and the quality of interfaces is a very challenging objective which registers a continuous progress. Also the development of nanostructured oxides electrolytes have demonstrated a strongly enhanced interfacial ionic conductivity which appears very promising for further reduction of the working temperature in SOFC. Advanced characterization techniques, such as 3D tomography, greatly contribute to this purpose. An emerging application of such a devices is to use them in the reverse mode for chemical energy storage purposes. The emerging hydrogen economy and its competitiveness in transportation or static
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Hydrogen storage is one of the main concerns for any transport use of this fuel, the progress in nanoscience and simulation to unveil the capabilities of many types of materials to surpass the many encountered challenges: nanoscale materials to minimize diusion length and time, catalytic eciency of molecular hydrogen splitting, chemical bonding, structural and microstructural eects on hosts (light alloys or molecular compounds). A broad horizon has been opened with such a demanding challenge which now faces a new era for achieving the required performances.

applications, and its practical complementarities and synergy with electricity as energy carrier, strongly rely on the advances in preparing nanostructured materials because all the mentioned processes require interfacial gassolid ionic and electronic exchanges among dissimilar materials.

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Light harvesting eciency and several nanoscale processes dominate the eciency of such cells, mainly in those classied in the 2G and 3G groups. Charge generation (exciton formation, electron hole pair separation) and charge transport to the corresponding electrodes avoiding recombination are the key issues. Many dierent types of fully molecular organic materials or hybrid organic inorganic are being investigated as nanocomposite blends; p-type conjugated polymers and n-type fullerene blends display the highest performance up to now (~8%). Hybrid cells with p-type nanostructured inorganic semiconductors and ptype organic semiconductors are now being deeply investigated. All these cells can be processed through low cost techniques such as solution spin coating or ink jet printing. The main issue here is to improve the quantum eciency of light transformation, avoiding charge recombination at defects and long term degradation of the polymers. A very extensive worldwide eort is being undertaken in this area with emphasis on new molecular blends and device processability with the purpose of reaching an enhanced eciency and the cost threshold of 0.3 /W. 3G multijunction cells consists mainly on III-V semiconductor stacks grown by MBE or MOCVD, they absorb a wide spectrum of visible light and hence overcome the thermodynamic limit of 1G cells. New concepts such as multiphoton absorption through quantum nanodots and hot carrier generation have fostered new nanotechnology based devices and so this area is very active at present in relationship to the interest of developing MW-class photovoltaic solar generators with power concentration ratios near 1000. The idea of using self-assembled colloidal semiconductor nanodots as solar energy generators has been also recently raised and its enormous potential has been widely stressed. As a last route to low cost cells we should
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mention dye-sensitized solar cells (DSC), rst introduced by Grtzell. These cells use nanocrystalline oxide semiconductors (nanoporous, nanorods) in contact with organic dyes which generate electrons through a photochemical reaction. These DSC cells have the advantage of a low cost while they have already achieved eciencies beyond 10%. They are very well adapted to the needs of large area applications, such as in buildings. About 40% of the solar spectrum belongs to be IR range while about 50% of the primary energy ends up as heat. Therefore, there is an extremely large room for direct recycling of such energy into electric generation through thermoelectric devices. This old phenomenon has recently seen an outstanding revival due to the discovery of either new materials or the development of nanostructured materials where the conicting functionalities can be combined. Thermoelectrical power, electrical and thermal conductivity can be controlled through quantum size eects and hence semiconducting nanowire engineering has turned out an emerging research eld demanding deep consideration. As a nal technology with a large potential to reduce energy consumption and CO2 emissions through enhanced eciency we should mention lightening materials (~20% electricity consumption worldwide). Inorganic semiconductor LEDs and OLEDs are being widely investigated as solid state systems which promise a deep worldwide revolution because of its enhanced eciency. Increase of eciency and lifetime, as well as the development of white light generation, all at low cost, are the more challenging objectives in this eld. The use of phosphors to convert UV light into visible light is also a very promising route. Overall the present roadmaps indicate that in 10-20 years LEDS will be the dominant technology and hence many materials

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2.3 Electrical energy Electrical energy has been continuously increasing its share as energy vector since its implementation, achieving at present values near 40%. It is expected that this process will continue in the future. Particularly the cleanness of this vector greatly facilitates its use in transport systems (at present associated to 30% of the total fossil fuel consumption). Additionally, the increasing demand of enhanced reliability and power quality, even with a strong increase of the intermittency of renewable generation, has raised the concept of smart grids where new semiconducting power electronics and superconducting power systems are needed. Even though, the issue of achieving ecient electricity storage systems continues to be a key issue for any future development of this energy vector. We will therefore review as well electrochemical energy storage systems such as batteries and supercapacitors. Electrical batteries and supercapacitors cover a wide spectrum of the Ragone diagram (power density energy density) and the improvement rely on a full understanding of the electrical and electrochemical processes in relationship with the structural and chemical transformations at the nanoscale. Li ion batteries are the most promising systems for hybrid and electrical cars and so the major developments are associated to electrodes for Li insertion. A major concern is to avoid material aging during the charge discharge processes and to reduce the required time. These issues have been found to be much reduced in oxide or phosphate electrodes with nanometric dimensions (nanowires, nanoparticles) where lattice expansion do not degrade the performances. Conicting functionalities can be
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Supercapacitors are based on high surface area nanomaterials where the idea of a double layer charge accumulation is implemented very eciently. These systems can be assimilated to a set of series capacitor system where the electrical charge is accumulated at the electrode interfaces. The main advantage of these storage systems is their fast charge discharge times (only electronic charge transport is involved, no chemical reaction) and hence they are useful complements to conventional batteries (accumulation of car breaking energy for instance). Conversely, only a low energy density has been achieved up to now, although new ideas are promising to enhance it. The most widely investigated materials for such systems are Carbon based porous materials (nanotubes, bres, etc.) although other alternatives such as anodized alumina membranes coated with metals (ALD) or mesoporous transition metal oxides have recently appeared as very ecient materials with potential for increasing also the energy density. A particular concern in such nanoporous materials is to achieve a tight control of the pore size. Superconducting materials have generated a boost of new ecient and reliable power systems having a huge potential for smart electrical energy distribution, energy storage and generation and nal use (motors).

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developments with nanostructure control will be required. Particularly, novel wide band gap semiconductors such a ZnO or some nitrides are being widely investigated.

very often overcome through the development of nanocomposite materials which can combine high electronic conductivity with a fast and safe Li ion insertion capability, thus becoming a very promising route to new advanced battery systems. Nanoscale interfacial and strain characterization together with in-situ structural modication analysis of materials bearing a high degree of disorder are key problems requiring convenient tools such as HRTEM and scattering techniques (neutrons, synchrotron radiation).

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The key development for a fast market penetration is to fabricate long-length nanostructured conductors at low cost, mainly through chemical deposition methodologies. The most promising materials are at present the so called 2nd generation (2G) coated conductors, based on YBa2Cu3O7 (YBCO). The rst goal has been to avoid the detrimental eect of grain boundaries on critical current density and this has already been achieved through clever methodologies to develop oxide epitaxial layers on metallic substrates while keeping structural control at the nanoscale. Industrial production of 2G conductors over km lengths has been already demonstrated although much more eort is still required to simplify their architecture and hence reduce the cost. A second boost on performance of 2G superconductors has been recently demonstrated through the development of nanocomposite lms and conductors. The goal here is to create a network of nanometric nonsuperconducting phases (nanodots, nanorods) within the superconducting matrix which pin vortices and hence increase the critical current at high temperatures and under high magnetic elds. Understanding the growth mechanisms of complex oxide nanocomposites and the inuence of induced strain on the superconducting properties is one of the present bottlenecks for further development of materials with enhanced performance. For the rst time, the performance of these nanostructured superconductors has surpassed at 77OK those of low Tc superconductors at liquid He temperature. Very high magnetic elds are expected to be created for magnets (fusion), generation (wind energy), motors (ships) and energy storage
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systems. In spite of the remarkable progress already achieved, there is still a large margin for improvement because the theoretical limits of these materials are still well above the achieved critical currents. Its particularly essential to understand properly the relationship between nanostructure and vortex pinning properties. These conductors have demonstrated current densities 10 times higher than Cu and so the development of high power underground cables (5-7 times conventional wire power) is one of the closest priorities, together with Fault current limiters to reach a smarter grid allowing to integrate the renewable energies The worldwide roadmaps dened up to now suggests a progressive penetration of this new technology in the market of power systems in the next 10-20 years. 3. International publications (2007-2009) A selection of publications spanning all the elds mentioned before is reported here. J. Gutirrez, A. Llords, J. Gzquez, M. Gibert, N. Rom, S. Ricart, A. Pomar, F. Sandiumenge, N. Mestres, T. Puig and X. Obradors. Strong isotropic flux pinning in solutionderived YBa2Cu3O7-x nanocomposite superconductor films. Nature Materials, 6 (2007), pp. 367-373. B. E. Hardin, E.T. Hoke, P.B. Armstrong, J.H. Yum, P. Comte, T. Torres, J.M.J. Frechet, M.K. Nazeeruddin, M. Gratzel and M.D. McGehee Increased light harvesting in dye-sensitized solar cells with energy relay dyes. Nature Photonics, 3 (2009), pp. 406-411. H. Gommans, T. Aernouts, B. Verreet, P. Heremans, A. Medina, C.G. Claessens, G Christian and T. Torres. Perfluorinated Subphthalocyanine as a New Acceptor Material in a Small-Molecule Bilayer Organic Solar Cell.

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Advanced Functional Materials, 19 (2009), pp. 3435-3439. M. R. Palacn. Recent advances in rechargeable battery materials: a chemist's perspective. Chemical Society Reviews, 38 (9), (2009), pp. 2565-2575. G. F. Ortz, I. Hanzu, T. Djenizian, P. Lavela, J. L. Tirado and P. Knauth. Alternative Li-Ion Battery Electrode Based on Self-Organized Titania Nanotubes. Chemistry of Materials, 21 (2009), pp. 63-67. M. Gibert, T. Puig, X. Obradors, A. Benedetti, F. Sandiumenge and R. Hhne. Self-organization of heteroepitaxial CeO2 nanodots grown from chemical solutions. Advanced Materials, 19 (2007), pp. 39373942. J. Gutirrez, T. Puig, M. Gibert, C. Moreno, N. Roma, A. Pomar and X. Obradors. Anisotropic c-axis pinning in interfacial selfassembled nanostructured trifluoracetateYBa2Cu3O7-x films. Applied Physics Letters, 94 (2009), art. 172513. F. Fabregat-Santiago, J. Bisquert, L. Cevey, P. Chen, M.K. Wang, S.M. Zakeeruddin, M. Shaik and M. Gratzel. Electron Transport and Recombination in Solid-State Dye Solar Cell with Spiro-OMeTAD as Hole Conductor. Journal of the American Chemical Society, 131 (2009), pp. 558-562. J. lvarez-Quintana, X. lvarez, J. RodrguezViejo, D. Jou, P.D. Lacharmoise, A. Bernardi, A.R. Goni and M.I. Alonso. Cross-plane thermal conductivity reduction of vertically uncorrelated Ge/Si quantum dot superlattices. Applied Physics Letters, 93 (2008), art. 03112. J. Garca-Barriocanal, A. Rivera-Calzada, M. Varela, Z. Sefrioui, E. Iborra, C. Len, S. J.

S.A. Haque, S. Koops, N. Tokmoldin, J. R. Durrant, J. S. Huang, D.D.C. Bradley and E. Palomares. A multilayered polymer light-emitting diode using a nanocrystalline metal-oxide film as a charge-injection electrode. Advanced Materials, 19 (2007), pp. 683-687. R. Otero, D. Ecija, G. Fernndez, J. M. Gallego, L. Snchez, N. Martin and R. Miranda. An organic donor/acceptor lateral superlattice at the nanoscale. Nano Letters, 7 (2007), pp. 2602-2607. R. M. Navarro, M. C. Snchez-Snchez, M. C. Alvarez-Galvn, F. del Valle and J. L. G. Fierro. Hydrogen production from renewable sources: biomass and photocatalytic opportunities. Energy & Environmental Science, 2 (2009), pp. 35-54. S. Colodrero, A. Mihi , L. Haggman , M. Ocana, G. Boschloo, A. Hagfeldt and H. Miguez. Porous One-Dimensional Photonic Crystals Improve the Power-Conversion Efficiency of Dye-Sensitized Solar Cells. Advanced Materials, 21 (2009), pp. 764-770. I. Gonzlez-Valls and M. Lira-Cantu. Vertically-aligned nanostructures of ZnO for excitonic solar cells: a review. Energy & Environmental Science, 2 (2009), pp. 19-34. 4. Initiatives to be undertaken in Spain within the period 2010-2013 The R&D activities related to the energy sector have remained much dispersed up to now while it has become critical nowadays to achieve a critical mass in those domains where there is

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Pennycook and J. Santamara. Colossal ionic conductivity at the interfaces of epitaxial ZrO2:Y2O3/ SrTiO3 heterostructures. Science 321 (2008), pp. 676-680.

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clear technological demand. The chain value for energy related issues is very wide, spanning from nanoscience and advanced materials, to materials engineering, systems development and integration and nal use, including market pull views and regulations. It is clear that Spain has a large oer of companies related to the nal use of energy which can play a catalytic role for the whole chain value mentioned above. Also specic regulation and governmental actions can decisively foster the industrial dynamism of this sector. Unless decisive actions are taken to promote the transformation of more traditional industries into this new sector and to create new high-tech companies it is very likely that the nal user companies will base their business fully on materials, components and devices produced abroad. It is also worth to stress, however, that this is a global business and so in most of the cases the Spanish industry will need to be integrated into European initiatives in order to have a global size. Hence it becomes very important to establish strategic actions and alliances much before than any product becomes a commercial reality. In most of the cases the research groups being active in Spain in the areas mentioned within the State of the art section have not achieved enough critical mass to become leaders in the international scene, even if in many cases the research activities carried out have a very signicant impact. The establishment of larger research projects, such as the Consolider programs, has helped to a certain degree to overcome this limitation. Still, however, these programs have not been accompanied by the necessary investments on infrastructures and so the expected outputs
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should be limited. Additionally, the link between these research-based programs and the existing development and valorization programs is very weak and it should be strengthened. Properly addressed roadmaps integrating the multiple initiatives would certainly help to maximize the overall eciency of the R+D+i system. The research activities on Nanomaterials for energy require quite specic equipments and facilities and very often the implementation of research centers on Nanoscience and nanotechnology do not cope adequately with these specic needs. The bottom-up approach characterizing these activities require specic laboratories, equipments and advanced characterization facilities which are not being properly attended up to now. It is also worth to stress the need of signicant eorts on multiscale nanomaterials simulation to cope with the complexity of the many phenomena involved. It is important to point out as well the need, in the very early stage of development, of scalingup the production of nanomaterials in order to integrate them in demonstrators of systems or devices for further engineering development needs to be properly considered. The demonstration stage is essential in this area; otherwise the new technology penetration is delayed and the capability of innovation through technology transfer is lost. On the other hand, the eld of Nanomaterials for energy requires an accelerated action to prepare highly skilled personnel; otherwise there will a very important shortage of trained scientists and technologists in a wide span of new technologies being developed. It is therefore very important to dene priorities for

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PhD fellowships, postgraduate courses and technical sta recruitment. In conclusion, the proposed priority actions to be considered to foster a successful R&D&i in the area of Nanomaterials for energy are the following: To define a few specific areas and laboratories (or networks) where research actions including nanoscience-based materials are taken with the purpose of integrating the full chain of value. The definition of mid and long term roadmaps should be a specific requirement of this initiative. The goal will be to achieve a scientific and technological leadership position. The initiatives should involve scientific groups with the required know-how and industries from the whole chain of value, from the manufacturing sector to the final users, including the corresponding system development companies. The initiative should have also as an objective to promote the creation of spin-off companies to develop the scientific advances worth of being commercialized and to handle an aggressive IPR policy. To establish advanced research facilities in nanoscience with open access and adapted to the required bottom-up nanofabrication needs. Also to generalize the implementation of advanced characterization facilities such as Nanoscopy spectroscopy centers with the necessary equipment and technical skills to cope with the demand of research having very specific features relevant to this field. To engage specific actions to attract highly motivated students to the field of nanomaterials for energy and energy technologies in general. Outreach activities stressing the potential of nanoscience to

address the energy challenge should be strongly promoted. 5. Required infrastructure to reach the objectives (2010-2013) Nanofabrication units adapted to the requirements of the materials for energy, mainly based on bottom-up approaches. Specifically, clean room areas with tools adapted to the chemical processes and in-situ characterization methodologies should be made available. These facilities should allow individual researchers and small research groups to explore new ideas fast and using the most advanced methodologies. Advanced characterization facilities with capabilities adapted to the specific characteristics of the nanomaterials for energy. Electron nanoscopic research is a particularly useful area because compositional and structural analysis may be performed altogether. Very significant advances have been made recently in this area (aberration correction microscopes in transmission and scanning modes) which requires a decisive action to keep the pace in the international scene. Three dimensional microstructure imaging analysis by electron tomography is also becoming a useful tool for the complex arrangement of components including nanomaterials for energy. Advanced tools for sample preparation are also needed to make a full use of these methodologies. The use of the new synchrotron radiation center ALBA will also help to carry out advanced structural and spectroscopic analysis of energy-related nanomaterials. Finally, specific physical and chemical characterization tools with nanoscale analysis adapted to the complex functionalities of energy-related materials should be more widely implemented and/or developed.
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Mid-size materials fabrication laboratories integrating the developments on nanomaterials. These laboratories are very specific but they are a key requirement to achieve a mature development for any new emerging technology. Materials engineering skills are required and their implementation should help to gain the required vertical integration of the whole chain of value. 6. Relevant initiatives and projects Several materials research projects of the National Research Plan (Materials and Nanoscience strategic action) are related to the area of nanoscience in energy-related topics. Also many master courses devoted to energy research are already offered by several Universities in Spain. A significant part of these masters include materials related issues. Only a few examples of large research projects related to nanomaterials for energy are mentioned here. 6.1 Spain CONSOLIDER Projects Research on a New Generation of Materials, Cells and Systems for the Photovoltaic Conversion (GENESIS-FV). CSD 2006-00004, Coordinator: Luque Lpez, Antonio, Center: Instituto de Energa Solar de la Universidad Politcnica de Madrid. Hybrid Optoelectronic and Photovoltaic for Renewable Energy (HOPE). CSD 2007-00007, Coordinator: Juan Bisquert Mascarell, Center: Escuela Tcnica Superior de Ingeniera de la Universidad Jaume I, Castelln.

Molecular nanoscience (NANOMOL). CSD 2007-00010, Coordinator: Eugenio Coronado Miralles, Center: Instituto de Ciencia Molecular de la Universidad de Valencia. Advanced materials and Nanotechnologies for innovative Electrical, Electronic and magnetoelectronic devices (NANOSELECT). CSD 2007-00041, Coordinator: Xavier Obradors Berenguer, Center: CSIC Instituto de Ciencia de Materiales de Barcelona. Advanced Wide Band Gap Semiconductor Devices for Rational Use of Energy. CSD 2009-00046, Coordinator: Jos Milln Gmez, Center: CSIC Centro Nacional de Microelectrnica. Developments of more efficient catalysts for the design of sustainable chemical processes and clean energy production. CSD 2009-00050, Coordinator: Avelino Corma, Center: CSIC Instituto de Tecnologa Qumica. Additionally, it is worth to mention that several new research centers have been implemented in Spain related to the topics mentioned in this report. New research centers in Spain LInstitut de Recerca de lEnergia de Catalunya (IREC). New energy research center, Catalonia. Centro de Investigacin Cooperativa CIC energiGUNE. New energy research center, Basque Country. IMDEA Energa. New research center, Madrid. 6.2 Europe A selection of EU based projects in the fields with Spanish participation: High performance nanostructured coated conductors by chemical processing (HIPERCHEM). NMP3-CT-2005-516858, 2005-2008,
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Coordinator: ICMAB-CSIC. Efficient environmental-friendly electroceramics coating technology and synthesis (EFECTS). EFECTS-205854-1, 2008-2011, ICMAB-CSIC. Development and field test of an efficient YBCO Coated Conductor based Fault Current Limiter for Operation in Electricity Networks (ECCOFLOW). ECCOFLOW-241285, 2010-2013, ICMAB-CSIC, Endesa, Labein. Modelling of interfaces for high performance solar cell materials (HIPERSOL). HIPERSOL-228513, 2009-2012, ISOFOTON, S.A. Development of photovoltaic textiles based on novel fibres (DEPHOTEX). DEPHOTEX-214459, 2008-2011, CETEMMSA, CENER-CIEMAT, Asociacin de la Industria Navarra. Intermediate band materials and solar cells for photovoltaics with high efficiency and reduced cost (IBPOWER). IBPOWER-211640, 2008-2012, Universidad Politcnica de Madrid. Efficient and robust dye sensitzed solar cells and modules (ROBUST DSC). ROBUST DSC-212792, 2008-2011, Institut Catal dInvestigaci Qumica, Universidad Autnoma de Madrid. Smart light collecting system for the efficiency enhancement of solar cells (EPHOCELL). EPHOCELL-227127, 2009-2013, Acondicionamiento Tarrasense Asociacin, MP Bata Consultoria Medioambiental S.L. CIDETE Ingenieros S.L., Universitat Politecnica de Catalunya. NAnostructured Surface Activated ultra-thin Oxygen Transport Membrane (NASA-OTM).
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NASA-OTM-228701, 2009-2012, Instalaciones INABENSA, S.A., CSIC. Nanostructured Electrolyte Membranes Based on Polymer-Ionic Liquids-Zeolite Composites for High Temperature PEM Fuel Cell (ZEOCELL). ZEOCELL-209481, 2008-2010, Universidad de Zaragoza, Celaya Emparanza y Galdos SA, CIDETEC. Nanotechnology for advanced rechargeable polymer lithium batteries (NANOPOLIBAT). FP6-NMP-2004-33195, 2006-2009, Institut de Cincia de Materials de Barcelona (ICMABCSIC). Large-Area CIS Based Thin-Film Solar Modules for Highly Productive Manufacturing (LARCIS). FP6-SUSTDEV-19757, 2005-2009, Universitat de Barcelona. Advanced Thin-Film Technologies for Cost Effective Photovoltaics (ATHLET). FP6-SUSTDEV-19670, 2006-2009, Centro de Investigaciones Energticas, Medioambientales y Tecnolgicas. Ionic liquid based Lithium batteries (ILLIBATT). FP6-NMP-2004-33181, 2007-2010, Celaya Emparanza y Galdos SA, CIDETEC. Advanced lithium energy storage systems based on the use of nano-powders and nanocomposite electrodes/electrolytes (ALISTORE). FP6-SUSTDEV-503532, 2004-2008, Institut de Cincia de Materials de Barcelona (ICMABCSIC), Universidad de Crdoba. 7. Conclusions Spain is particularly well positioned in the international scene in the eld of energy technologies, with several companies and industrial sectors being widely recognized for its

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innovative prole. Research in energy technologies and materials related issues, particularly nanoscience and nanotechnology, is now very stringently promoted worldwide, linked with the urgent need of addressing the energy challenge of the 21st century. Therefore, it is clear that its strategically very important to position the R&D&i in nanomaterials for energy as a priority. A certain number of initiatives have been already engaged to develop the above mentioned potential, however, there are still many drawbacks in the coordination of initiatives and in the denition of priorities which have been described here in a certain detail. For sure, nanomaterials for energy brings a timely and unique opportunity for innovation which Spain can not miss, mainly taking into account the present need for a turning point in our economic model.

N.S.Lewis, Powering the planet, MRS Bulletin 32, 808 (2007).

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Climate change 2007, Intergovernmental Panel on Climate Change report, Cambridge Univ. Press (2007) (www.ipcc.ch).

R. E. Smalley, MRS Bulletin 30, 412 (2005); D. J. Nelson, M. Strano, Nature Nanotechnology 1, 96 (2006). Alternative energy technologies, Nature 441, 332 - 377 (2001). Harnessing Materials for energy, MRS Bulletin 38, 261 - 477 (2008).
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References
1

Novel materials for energy applications, European Comission, I. Vouldis, P. Millet and J.L. Valls eds. (2008). (http://ec.europa.eu/research/industrial_ technologies/).

US Department of Energy reports (www.sc.doe.gov/bes/reports)

Toward a Hydrogen economy, Science 305, 957 1126 (2004). A. P. Malozemo, Nature Materials 6, 617 (2007).
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Basic research needs to assure a secure energy future Workshop on solar energy utilization Basic research needs for the Hydrogen economy Basic research needs for superconductivity Basic research needs for Solid state lighting Basic research needs for electrical energy storage Grid 2030: a national vision for electricitys second 100 years Transforming electricity delivery Strategic plan (2007). Climate change, Science 302, 1719 - 1926 (2003).
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Climate change, Nature 445, 578 - 582 (2007).

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> JOSEP SAMITIER Place and date of birth Barcelona (Spain), 1960 Education M.S. Degree; Physics; Barcelona University. Ph.D Degree; Physics; Barcelona University. Thesis Title: GaAs MESFET Devices and electrooptical characterization of III-V semiconductors. Profesional Experience Full Professor of Electronics, Barcelona University. Chair of Department of Electronics, Barcelona University. Director of the Nanobioengineering Laboratory (IBEC). Director of Bioengineering Section. Barcelona Science Park. Deputy head Electronic Engineering School. Visiting Professor LAAS (Toulouse). Assistant professor of Electronics. Visiting research fellow at the Philips Electronic Laboratory (LEP) Paris (France). Honors and Awards Barcelona city Prize in the area of technology. jsamitier@ibecbarcelona.eu

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NANOMEDICINE

1. Introduction Nanomedicine has emerged as a novel eld which involves the application of nanotechnology to human health. Various therapeutic and diagnostic modalities have been developed which can potentially revolutionize disease diagnostic and treatment. The knowhow in nanotechnology oers new ways to create better laboratory diagnostic tools for non-invasive screening. Accurate and early diagnosis, will facilitate timely clinical intervention and can mitigate patient risk and disease progression. The conventional oral and parental routes of drug administration have several disadvantages owing to altered pharmacokinetic parameters and wide spread distribution. Targeted delivery of drugs, nucleic acids and other molecules using nanoparticles are the focus of current research and development. The goal of tissue engineering or regenerative medicine is the improvement, repair, or replacement of tissue and organ function. The ultimate goal is to enable the body to heal itself by introducing and engineered scaold that the body recognizes as own. The challenges are not minor. If nanotechnology is to be translated into meaningful benets for patients, innovation in the laboratory must be supported by the pillars of evidence based medicine and predictable regulatory pathways.

2. State of the Art nanomedicine (from the nanomedicine roadmap 2020) 2.1 Regenerative Medicine A really broad denition of Regenerative Medicine includes the repair, replacement, or regeneration of damaged tissues or organs with a combination of several technological approaches, which can be roughly devided into two subareas: smart biomaterials and advanced cell therapy. Smart Biomaterials Since 2006, research on biomaterials has fostered many steps forward and signicant changes on the tissue regeneration approach. Major attention has been given to the importance of biomaterial mode of action. Research eorts have moved from the development of inert polymers which mimic the biomechanical properties of native tissue to bioactive materials which promote the tissue self healing. The development of smart biomaterial can be divided into two phases: discovery and process optimization. In the discovery phase, the main issue is product characterization. 3D functional assays and devices to measure intracellular signals are useful tools in this phase. The process optimization phase involves the translation of prototype into product assuring scalability, quality, and safety of the proposed treatment.

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Cell therapies From May 2005 the European Commission prepared several draft regulation intended to harmonize in EU the legislation on human tissue engineered products. The nalization of a common European regulatory framework required slow and complex public consultation, which ended in September 2008 with the publication of the nal guidelines. The development of an eective cell therapy includes dierent phases: the identication of best materials for cell transplantation and the optimization of the production process. The rst phase takes into account the development and characterization of dierent devices for cell transplantation. The process optimization phase involves quantifying the relationship between culture parameters and cell output, as well as research on scale-up. The third phase consists of toxicology assessment and quality control for therapeutic delivery of the cell product. Cell-materials compounds or engineered tissues can be considered as a delivery system where the cells are immobilised within polymeric and biocompatible devices and secrete therapeutic products. In this light, drug delivery control is a key parameter for the development of a new medicine. Research on biomaterials has been focused on the design of safe and manufacturable technologies for the local and systemic delivery of therapeutic molecules from the enclosed cells. 2.2 Drug Delivery (Nanopharmaceutical and Nanodevices) One area identied of being crucial for future breakthroughs is the area of Nano-encapsulation or nanodelivery systems that have a signicant therapeutic payload and are capable of being transported through biological barriers. Such

particles should be biocompatible and acceptable to regulatory agencies e.g. not retained in the body, even if inert. Therapeutic particles should be relatively inexpensive, manufacturable, acceptable to regulators, and stable to storage. Another topic will be that of transporters or technologies capable of moving therapeutic nanoparticles across biological membranes, tissues or organs at a transport rate such that therapy can be eective. For proteins for example this lies in the range of 10 mgs per day orally. Besides that, the choice of the delivery route or the barriers to be crossed will be important, e.g. Intracellular, Dermal, Oral, Pulmonary, Blood Brain Barrier. This choice will determine the technologies applicable. Another factor to be addressed will be the bioavailability of macromolecule which has to be larger than 10%. The choice of the therapeutic modality will be essential. This could include proteins, antibodies, nucleic acids, peptide mimetics, PNAs, foldamers, non-Lipinski molecules and materials that require some external activation such as ultrasound. Small molecules could also be included but they normally already have a good bioavailability and expensive delivery technologies may not be reimbursed making them probably a lower priority. To bring to the market new therapeutic modalities or to expand the current clinical uses of biologicals therapeutic entities such as nucleic acids are required. Such new therapeutic classes should oer radical improvements in the treatment of dicult diseases. 2.3 Diagnostics The area of diagnostics can be divided into in vivo and in vitro technologies. In both areas the goal is to detect an evolving disease as early as

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possible up to the point of detecting single cells or biomarkers indicating the onset of a disease. Major objectives are the development of: Devices for combined functional imaging, structural and

development. The trend here is clearly on implementing these imaging modalities alone or in combination. Miniaturization of imaging devices and improvement of technical specications of existing imaging systems can be achieved thanks to nanotechnology. In the perspective of developing a lightweight, small footprint CT6 system, a proposed disruptive technology uses carbon nanotube based X-Ray sources in CT to shrink the size of the complete systems. This would allow to bring CT to the doctors oces or even to ambulances. On the opposite, baby cyclotrons seem to be out of reach. In vivo imaging can also be used for guiding therapy with MR, PET, Optical and X-ray/CT, MRgFUS for biopsy and drug release. Targeted therapy is expected to lead to improved quality of healthcare, in reducing treatments with unsatisfactory patient outcome or with adverse eects. Reducing the concentration of contrast agents is one means to reduce costs. The characteristics of contrast agents (size, composition, coating, and physical properties) can be adjusted to respond eciently to design requirements, for instance for a better sensitivity and specicity. Another option is to design or develop a contrast medium capable of serving several modalities. This could consequently also reduce the volumes and reinjection rates. In fact, these contrast agents which can be used in dierent modalities separately or combined in a multimodality approach are highly desirable. New types of carriers for contrast agents are envisaged such as magnetic nanoparticles or even empty viruses or magnetic bacteria. Magnetic particles would oer higher eciency due to narrower magnetic characteristic distribution, precise control of magnetic

Devices for multi parameter measurement (multiplexing), Devices for monitoring personalized medicine. therapy and

In the In vivo imaging area some substantial challenges have been identied. One of the foremost obstacles is the diculty in obtaining an approval of new and innovative contrast agents. This includes obviously also the necessity to conrm the benets for the patients. Challenging is as well the task to further improve the imaging equipment as such and not to forget the training of endusers. Nanotechnology can contribute to the development of the in vivo imaging area by two means: Improving the existing and/or discovering new quantitative imaging systems. Developing new contrast enhancing contrast. agents for

The benets expected from nanotechnology are mainly based on the physical and chemical properties of novel materials at the nanoscale. However, the development of nanotech based in vivo imaging also depends on several nontechnical parameters like, regulatory approval of contrast agents, education and training of healthcare operators and healthcare reimbursement policy. While some conventional imaging modalities like PET1, MRI2, SPECT3, US4, are revisited by nanotech, some new imaging modalities like the MPI5 method (by Philips) are currently under
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properties, and an inherent potential for lower costs. The production of magnetic nanoparticles could also be envisaged by biomimetic templating. Another category of nanoscale particles are crystalline nanoparticles used for therapeutic purposes or for diagnostic applications in combination with external devices such as MRI, Laser, Radiotherapy, CT Scan, Ultrasound, HF, etc. In particular the up-scaling of the production methods for contrast agents is thought to provide a great economic potential that could create substantial economic returns. 3. International publications If you introduce the world nanomedicine in the web (www.gopubmed.com/web/gopubmed) we obtain 1,388 documents distributed. We observe that Spain is in the second position after USA, and Barcelona is the second city after Boston. Its dicult to remark the most important paper published, so we prefer to summire the best results and challenges of nanomedicine published in some review and opinion papers as:

Seven Challenges for nanomedicine, Nature nanotechnology Vol 3 May 2008. Emerging trends of nanomedicine an overview, Fundamental & Clinical Pharmacology 23 (2009) 263-269. Translational nanomedicine: status asessement and opportunities, Nanomedicine Vol 5 (2009) 251-273. Designer Biomaterials for nanomedicine, Adv. Funct. Mater 2009 19 3843-3854. Detecting rae cancer cells, Nature nanotechnology, Vol 4 Dec 2009 798-799. Nanomedicine challenge and perspectives, Angew. Chem. Int. 2009 48, 972-897. Nanomedicine: perspective and promises with ligand-directed molecular imaging, European J. of radiology 70 (2009) 274-285. 4. Initiatives Nanomedicine European Technology Platform (ETP) The Nanomedicine ETP is important initiative led by industry set up together with the European Commission. A group of 53 European stakeholders composed of industrial and academic experts established the European Technology Platform on nanomedicine in 2005. The rst task of this high level group was to write a vision document for this highly future-oriented area of nanotechnology-based health-care in which experts describe an extrapolation of needs and possibilities until 2020. At the beginning of 2006 the Platform was opened to wider participation (currently 95 member organisations) and has delivered a so-called Strategic Research Agenda showing a well elaborated common European way of working together for the healthcare of the future trying to match the high expectations that nanomedicine has raised so far. In 2009 the ETP

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published the Nanomedicine roadmap 2020: (www.etp-nanomedicine.eu/public). The Spanish Technology Platform on NanoMedicine (STPNM) is a joint initiative between Spanish industries and research centres working on nanotechnologies for medical applications. This initiative is supported by the Spanish government through the Centre for Industrial Technology Development (CDTI) and the Spanish Ministries of Science and Innovation (MICINN), Industry, Tourism and Trade (MICyT), and Health (MSC). The main objectives of the Platform are: Improve the collaboration within the Nanomedicine community in Spain avoiding fragmentation and lack of coordination, Promote the participation of Spanish stakeholders in international initiatives, from transnational cooperations to European projects, especially regarding the European Technology Platform, Establish recommendations concerning strategic research lines in the Nanomedicine field, Dissemination of Nanomedicine results to the scientific community and society-at-large. The focus of the Spanish Platform, with more than 150 members, is divided in ve strategic priorities: Nanodiagnostics; Regenerative Medicine; Drug Delivery; Toxicity and Regulation; and Training and Communication. This activity has facilitated a wide participation of Platform members in Spanish strategic research programmes run by the Spanish government through the Ingenio 2010 initiative. In September 2006 the Spanish Platform published a report focused on current status of Nanomedicine in Spain strategic vision of nanomedicine in Spain in order to establish research and development priorities and action
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plans on certain strategic issues to be solved in the medium to long term. (www.nanomedspain.net). The INGENIO 2010 programme aims to achieve a gradual focus of these resources on strategic actions to meet the challenges faced by the Spanish Science and Technology System. This gradual focus will be achieved by allocating a signicant portion of the minimum annual increase of 25% in the national R&D and Innovation budget to strategic initiatives grouped in three major lines of action: The CENIT Program (National Strategic Technological Research Consortiums) to stimulate R&D and Innovation collaboration among companies, universities, public research bodies and centres, scientific and technological parks and technological centres. The CENIT program cofinance major publicprivate research activities. These projects will last a minimum of 4 years with a minimum annual budgets of 5 million euros, where i) a minimum of 50% will be funded by the private sector, and ii) at least 50% of the public financing will go to public research centres or technological centres. The CONSOLIDER Program to reach critical mass and research excellence. CONSOLIDER Projects offers long-term (5-6 years), large scale (1-2 million euros) financing for excellent research groups and networks. Research groups may present themselves in all areas of know-how of the National R&D and Innovation Program. CIBER Projects promote high quality research in Biomedicine and Health Sciences in the National Health Care System and the National R&D System, with the development and enhancement of Network Research Structures. The CIBER-BBN is one of the new CIBER consortia in Spain, to encourage quality research and create a critical mass of

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researchers in the field of Biomedicine and Healthcare Sciences. The scientific areas represented within the CIBER-BBN are: Bioengineering and biomedical imaging, Biomaterials and tissue engineering and Nanomedicine, and the Centers research is focused on the development of prevention, diagnostic and follow-up systems and on technologies related to specific therapies such as Regenerative Medicine and Nanotherapies. (www.ciber-bbn.es). In addition to these three main programs, new research centers supported by regional administrations, support actions to increase human resources creating new stable research positions and a strategic scientic and technological infrastructures program are also included in the Ingenio 2010 initiative and in the research and innovation plan from the autonomous regions. 5. Conclusions Nanotechnology will have direct applications in medicine by contributing to improvements in health and life quality, while decreasing the economic impact. The report concludes that Spain can play a relevant role in the development of this eld because it has cutting-edge research centres, industrial and pharmaceutical sectors interested in using these new technologies as well as a health care system based on a network of hospitals with a very good basic and clinical research, interested in the development of translational research programs. Taking into account that the participation in the dierent instruments is in many cases incompatible, and the calls were open to all the Spanish science and technology system, these results conrm that the nanomedicine is a research priority in Spain and that exists a potentially strong sector to be developed in the next years.
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Glossary PET: Positron Emission Tomography MRI: Magnetic Resonance Imaging 3 SPECT: Single Photon Emission Computed Tomography 4 US: Ultra Sound 5 MPI: Magnetic Particle Imaging 6 CT: Computed Tomography
2 1

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> EMILIO PRIETO Place and date of birth Madrid (Spain), 1956 Education Mechanical Engineer by both ICAI-UPC (1981) and the Polytechnic University of Madrid (1982). Ph.D. by the Polytechnic University of Madrid, Department of Physics applied to Engineering (2007). Professional Career In 1982 joined the National Commission of Metrology and Metrotecnics. Since 1994, Head of Length Area at the Spanish Centre of Metrology. Member of the Consultative Committees for Length (CCL) and Units (CCU), of the International Committee of Weights and Measures (CIPM). Length Contact Person in EURAMET, Member of the International Society for Optical Engineering (SPIE), the Scientic Committee of NanoSpain, the Dimensional Metrology Committees from ENAC and AENOR CTN 82 and Chairman of the AENOR GET 15 Committee on Standardization on Nanotechnologies. eprieto@cem.mityc.es
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N A N O M E T R O L O G Y, N A N O - E C O - T O X I C O L O G Y A N D S TA N D A R D I Z AT I O N

1. Introduction Nanotechnologies enable scientists to manipulate matter at the nanoscale (size range from approximately 1 nm to 100 nm) 1. Within this size region, materials can exhibit new and unusual properties, such as altered chemical reactivity, or changed electronic, optical or magnetic behaviour. Such materials have applications across a breadth of sectors, ranging from healthcare to construction and electronics. Quantitative determination of properties of micro and nanostructures is essential in R&D and a pre-requisite for quality assurance and control of industrial processes. The determination of critical dimensions of nanostructures is important because the linking to many other physical and chemical properties depending on

such dimensions. To get quantitative measurements is essential to count with accurate and traced measuring instruments, together with validated measurement procedures widely accepted 2. Geometric features decisive for nanotechnology applications include 3D objects like large molecules (e.g. DNA), clusters of atoms (e. g. bucky balls), nanoparticles (like TiO2 particles added to products to improve reectivity), nanowires (like carbon nanotubes (CNT), singlewalled CNT (SWCNT), multi-walled CNT (MWCNT)), surfaces structures (superhydrophobic surfaces, riblets) and thin lms covering large surfaces (hardness, scratchresistance, reectivity, wetting properties ) 3. So, nanometrology, the science of measurement applied to the nanoscale plays a key role in the production of nanomaterials and nanometre devices. This has been recognized by many Governments, Research Institutions and the Private Sector across the World 4,5,6. There is no knowledge without accurate mesurements. Most of the todays eorts in Research are not successful and they wont be if there is no transfer to industrial applications. In fact, nanotechnology has not yet emerged as massive production due to both the diculty of developing a solid nanometrology infrastructure and the lack of
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Figure 1: 2D Standard

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awareness about it by researchers, product developers and R&D funders. But apart of potential benets to consumers, nanotechnologies may also present new risks that it is necessary to study, as a result of their novel properties. A report by the European Union Scientic Committee on Emerging and Newly Identied Health Risks (SCENIHR) published in 2009, listed a number of physical and chemical properties which aect the risk associated with nanomaterials 7, among them size, shape, solubility and persistence, chemical and catalytic reactivity, anti-microbial eects or aggregation and agglomeration. This is particularly important in the Food Sector. The European Union has provided 40 million in funding for nanomaterials safety research in the last three years, along with another 10 million in 2009. Studies on nano-eco-toxicology, together with standardization issues, are then important and urgent matters today at international level. 2. State of the Art 2.1 Nanometrology Instruments and techniques used today at the nanoscale are many and varied: exploration probes, ion beams, electronic beams, optical means, X-Ray, electromagnetic means, mechanical techniques, etc. New instruments oer every day better capabilities but such equipments should be correctly calibrated in order to maintain their metrological capabilities (traceability, accuracy) so guarantying the reliability of the results, something crucial in R&D and industrial production. Creation of metrological infrastructure, including the development of new calibration standards and measurement and characterization methods is not an easy task but it is intended for years by most of National Metrology Institutes (NMIs),

following specic R&D Programmes, as the European Metrology Research Programme (EMRP) 8, a long-term programme for high quality joint R&D amongst the metrology community in Europe, with a Phase 1 which started in 2007, supported by the European Commission through ERA-NET Plus, and a Phase 2 starting in 2010, supported through Article 169 of the European Treaty. Some of the EMRP Joint Research Projects (JRP) related to nanometrology are: Traceable Characterization of Nanoparticles, New Traceability Routes for Nanometrology or Nanomagnetism and Spintronics. The Spanish Centre of Metrology (CEM) participates since 2008 in some of these EMRP Projects.

Figure 2: Z-AXIS Step grating

A very important initiative on this eld of many NMIs since 2000 has been the development of metrological atomic force microscopes (MAFM). Today, there exist about 20 MAFM and 10 under construction all over the world. In Spain, CEM is also funding and running its own project to build a MAFM for the calibration of standards used at the nanoscale, integrating near eld microscopy and high resolution interferometric techniques based on stabilized

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laser sources traced to the national standard of length, for the benet of Institutes, R&D Centres, Universities and Industry. A EURAMET Workshop with participation of all teams currently working on - or that have worked on metrological AFM, will be held soon.

Spain is participating in some of the OECD Committees and Working Groups related to nanotechnology: Working Party on Chemicals, Pesticides and Biotechnology,
Working

Party Nanomaterials.

on

Manufactured

Working Party on Nanotechnology.

Figure 3: Grid Calibration AFM (Nanotec)

REACHEuropean Community legislation concerned with chemicals and their safe use plays also a role, albeit limited, in regulating nanomaterials. The general opinion today is that REACH can adequately regulate nanomaterials, but there is a need for future revisions of REACH to move the focus of regulation from the size/shape of nanomaterials to also their functionality 9. 2.3 Standardization

Very important also is the series of Conferences NanoScale (www.nanoscale.de) where, since 1995, the main developments on quantitative measurements at the nanoscale have taken place. These seminars on Quantitative Microscopy and Nanoscale Calibration Standards and Methods, taking place every two years, with open workshops of European research projects related to the Coordination of Nanometrology, have developed an increased number of methods and calibration standards to benet all users aware of instrumentation, no matter where they work (R&D, industry, Universities, etc.) helping them to maintain the traceability and accuracy of their instruments, and the reliability of the results. 2.2 Risk Assessment A forum where international coordination is taking place is the OECD. At the present time the OECD plays a central role in the coordination of research eorts for the development of test methodologies for risk assessment which will underpin the regulation of nanotechnologies.
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There is a key role for standardization as regards measurement and testing of the characteristics and behaviour of nanomaterials and the exposure assessment, complementing the work being carried out in the framework of the OECD and in the context of the implementation of REACH. The European Commission therefore requests CEN, CENELEC and ETSI to develop standardization deliverables applicable to a) Characterization and exposure assessment of nanomaterials and b) Health, Safety & Environment. Specically: 1. Methodologies for nanomaterials characterization in the manufactured form and before toxicity and eco-toxicity testing. 2. Sampling and measurement of workplace, consumer and environment exposure to nanomaterials.

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3. Methods to simulate exposures to nanomaterials. Spain is participating in the works of ISO/TC 229, CEN/TC 352 and IEC/TC 113 Committees through the AENOR GET 15 Committee. Matter under study is divided into four main elds: 1) Terminology and Nomenclature, 2) Measurement and Characterization, 3) Health, Safety and Environment and 4) Material Specications. Many technical Specications and International Standards are under production (about 40) [see Annex]. AENOR GET 15 Committee is composed at the moment by individual voluntary representatives of the following Institutions:
AENOR, CEM,

Propiedades materiales

fsicas

aplicaciones

de

INASMET Tecnalia, Centro Tecnolgico Instituto de Bioingeniera, Univ. Miguel

Hernndez

Instituto Nacional de Seguridad e Higiene en

el Trabajo (INSHT), Min. Trabajo e Inmigracin los Nanomateriales en la Construccin

LABEIN Tecnalia, Centro para la Aplicacin de Meggitt Nanogap Nanotec Electrnica S.L. Nanozar Plasticseurope Probra, Asociacin de productores de hilos y

Asociacin Espaola Normalizacin y Certicacin (Host) Centro Espaol (Chairmanship) de

de

bras sintticas, celulsicas y polmeros Inorgnica

Metrologa

Univ. Alcal de Henares, Dpto. Qumica

ACCIONA Infraestructuras Alphasip Avanzare CIC nanoGUNE, Centro de Investigacin en

Nanociencia (CSIC)

But it is important to involve many other Spanish Institutes, Platforms and stakeholders working in dierent aspects of nanotechnology to improve the coordination and contribute to produce the best technical specications for the ulterior benet of Spanish industries and citizens. 3. Most relevant international publications in the eld (2007-2009) Some of the international publications with the highest impact factor are the following ones. Nanometrology An Assessment of the United States Measurement System: Addressing Measurement Barriers to Accelerate Innovation, NIST Special Publication 1048, Jan 2007.

CCMA, Centro de Ciencias Medioambientales

Confederacin Espaola de CEPCO, Asociaciones de Fabricantes de Productos de Construccin

FEIQUE,

Federacin Empresarial de la Industria Qumica Espaola LEIA, Centro de Desarrollo Tecnolgico

Fundacin

Fundacin TEKNIKER GAIA, Asociacin de Industrias de Tecnologas Univ.

Electrnicas y de la Informacin del Pas Vasco Pblica de Navarra, Grupo de

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Journal of Research of the National Institute of Standards and Technology, US, Will Future Measurement Needs of the Semiconductor Industry be Met?, Jan 2007. Nanometrology of microsystems: traceability problem in nanometrology, Iuliana Iordache, D. Apostol, O. Iancu, et al., SPIE Proceedings, Vol. 6635: Advanced Topics in Optoelectronics, Microelectronics, and Nanotechnologies III, 663503, May 2007. Instrumentation, Metrology, and Standards for Nanomanufacturing, Michael T. Postek; John A. Allgair, Editors, SPIE Proceedings Vol. 6648, September 2007. Length calibration standards for nanomanufacturing, David C. Joy; Sachin Deo; Brendan J. Grin, SPIE Proceedings Vol. 6648, September 2007. Measurements of linear sizes of relief elements in the nanometer range using a scanning electron microscope, V. P. Gavrilenko; M. N. Filippov; Yu. A. Novikov; A. V. Rakov; P. A. Todua, SPIE Proceedings Vol. 6648, September 2007. Real-time sensing and metrology for atomic layer deposition processes and manufacturing, Laurent Henn-Lecordier, Wei Lei, Mariano Anderle, and Gary W. Rublo, J. Vac. Sci. Technol. B 25, 130 (2007). Nanometrology based on white-light spectral interferometry in thickness measurement, Huifang Chen, Tao Liu, Zhijun Meng, SPIE Proceedings, Vol. 6831: Nanophotonics, Nanostructure, and Nanometrology II, 683108, January 2008. Roadmap of European standardization, metrology and pre-normative research work for Nanotechnologies, NANOSTRAND Final Report, April 2008.

Feynmans Challenge: Building Things From Atoms One by One, E.C. Teague, Proceedings of the euspen International Conference Zurich - May 2008. Metrology at the nanoscale: what are the grand challenges?, Kevin W. Lyons, Michael T. Postek, SPIE Proceedings, Vol. 7042: Instrumentation, Metrology, and Standards for Nanomanufacturing II, 704202, September 2008. Digital Surf Newsletter: Focus on Spanish / French nanometrology programmes, Special Issue on Nanometrology, Nov 2008. White light interferometry applications in nanometrology, V. S. Damian, M. Bojan, P. Schiopu, et al., SPIE Proceedings, Vol. 7297: Advanced Topics in Optoelectronics, Microelectronics, and Nanotechnologies IV, 72971H, January 2009. Experimental study of nanometrological AFM based on 3-D F-P interferometers, Yu Huang, Ruogu Zhu, SPIE Proceedings, Vol. 7133: Fifth International Symposium on Instrumentation Science and Technology, 71334F, January 2009. OECD review of current science, technology and innovation policies for nanotechnology (Includes details on nanometrology, quality and standards activities), Inventory of National Science, Technology and Innovation Policies for Nanotechnology 2008, July 2009. UK Technology Strategy Board publication, Nanoscale Technologies: Strategy 2009-2012 Nov 2009. Co-Nanomet publication, European Nanometrology Foresight Review, Dec 2009.

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Nanotoxicity Toxicology of nanoparticles: A historical perspective, Gnter Oberdrster, Vicki Stone, Ken Donaldson, Nanotoxicology, 2007, Vol. 1, No. 1: Pages 2-25. Toxicologically Relevant Characterization of Carbon Nanomaterials, Robert Hurt and Agnes Kane, Division of Engineering Department of Pathology and Laboratory Medicine, Brown University, Providence, Rhode Island, Tri-National Workshop on Standards for Nanotechnology, National Research Council, Ottawa, February 2007. Ecotoxicology of Nanoparticles: Issues and Approaches, Georey Sunahara, Ph.D., Applied Ecotoxicology Group, Biotechnology Research Institute, Montreal, PQ, Canada, TriNational Workshop on Standards for Nanotechnology, National Research Council, Ottawa, February 2007. Biological activity of nanoparticles mechanisms of recognition and toxicity, Prof. Valerian Kagen, Univ. of Pittsburgh, Nanotech/DIT, Dublin, November 2007. Physical and chemical indicators of nanoparticle toxicity, Dr Gordon Chambers, Dublin Institute of Technology, Nanotech/DIT, Dublin, November 2007. Nanomaterials and nanoparticles: Sources and toxicity, Cristina Buzea, Ivan I. Pacheco, and Kevin Robbie, Biointerphases 2, MR17 (2007). Toxicology steps up to nanotechnology safety, Teeguarden JG, A Gupta, Escobar, P., Jackson, M. 2008. Research & Development magazine 50(1):28-29. PNWD-SA-7902. Emmission assessment for identication of sources and release of airborne manufactured

nanomatearials in the workplace: Compilation of existing guidance, Series on the safety of manufactured nanomaterials, Number 11, ENV / JM / MONO (2009) 16, June 2009. Report of an OECD Workshop on exposure assessment and exposure mitigation: Manufactured nanomaterials, Series on the safety of manufactured nanomaterials, Number 13, ENV / JM / MONO(2009)18, July 2009. Nano-silver-a review of available data and knowledge gaps in human and environmental risk assessment, Susan W.P. Wijnhoven, Willie J.G.M. Peijnenburg, Carla A. Herberts, Werner I. Hagens, Agnes G. Oomen, Evelyn H.W. Heugens, Boris Roszek, Julia Bisschops, Ilse Gosens, Dik Van De Meent, Susan Dekkers, Wim H. De Jong, Maaike van Zijverden, Adrinne J.A.M. Sips, Robert E. Geertsma, Nanotoxicology, 2009, Vol. 3, No. 2 : Pages 109-138. Nanotoxicology-A New Frontier, Lawrence J. Marnett, Chem. Res. Toxicol., 2009, 22 (9), p 1491, DOI: 10.1021/tx900261y, Publication Date (Web): August 20, 2009, Copyright 2009 American Chemical Society. Analytical methods to assess nanoparticle toxicity, Bryce J. Marquis, Sara A. Love, Katherine L. Braun and Christy L. Haynes, Analyst, 2009, 134, 425439. Standardization ISO/TR 27628:2007 Workplace atmospheres Ultrane, nanoparticle and nano-structured aerosols - Inhalation exposure characterization and assessment, 2007. ISO/TS 27687:2008 Nanotechnologies Terminology and denitions for nano-objects Nanoparticle, nanobre and nanoplate, 2008.

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International Workshop on Documentary Standards for Measurement and Characterization in Nanotechnologies, NIST, Gaithersburg, Maryland, USA, 2628 February 2008. Voluntary Measures in Nano Risk Governance, 4th International Nano-Regulation Conference, 1617 September 2008, St.Gallen (Switzerland), Conference Report, Christoph Meili, Peter Hrzeler, Stephan Knbel, Markus Widmer, The Innovation Society, Ltd, St.Gallen, Switzerland, www.innovationsociety.ch, September 2008. German Federal Institure for Materials Research and Testing (BAM), List of Currently Available Nanoscaled Reference Materials, Jan 2009. Documentary Standards Activity for Scanned Probe Microscopy, Ronald Dixson, NIST, 3rd TriNational Workshop on Standards for Nanotechnology, February 2009. Versailles Project on Advanced Materials and Standards (VAMAS), Technical Working Areas including Nanomaterials (Provides surveys of availability, consistency, repeatability and reproducibility of a range of material test methods), June 2009. International Organisation for Standardization Technical Committee 24, Subcommittee 4 (TC24/SC4: Particle Characterisation) Standards on Particle Characterisation, June 2009. 4. Actions to develop in Spain within the period 2010-2013 A general problem, not only in Spain, is that many people involved in nanotechnology are not aware about metrology and they do not feel the need of maintaining the traceability of their measuring instruments to support the reliability of their results which, in production, causes a lack of reproducibility and inhomogeneous products. For instance,

the concept of uncertainty of measurement is not well known yet. Other problem is that current measurement methods and standards are focused on relatively simple, idealised measurement situations. But there is room as well as a need to improve the basic metrological understanding of methods and standards. At the same time, research and standardization need to focus on more application oriented investigations of complex systems, and this will necessitate face a number of interdisciplinary issues. The Spanish High Council on Metrology (RD 584/2006, 12th May) advises and coordinates the full metrology in Spain in their scientic, technical, historical and legal aspects. At this High Council all Spanish Ministries are represented and, specically, those responsible of Industry, Trade, Environment, Food, Health, Science and Innovation; i.e., all those involved in nanotechnology and managing the National R&D Programmes. So, there is a nice opportunity to connect metrology to nanotechnology. Possible suggested actions are:
For the coming years the States eort to

enhance and coordinate all national activities related to nanotechnology (nanometrology, basic and applied R&D, risk assessment, standardization, etc.) must continue, but also involving the High Council on Metrology and AENOR. be independent, because matters have many faces (research, metrology, standardization). So, National Strategic Actions (for instance, Health and Nanotechnology) should be connected. The creation, as in other industrialized countries, of an Observatory for analysing periodically such connexion lines together with other

The dierent MICINN Strategic Actions can not

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aspects and needs of nanotechnology would be welcome.

Incorporate the metrological component in

all R&D projects. This is, for instance, mandatory for any new proposal on characterization methods submitted to ISO TC 229, being necessary to ll out a metrology check list in order to judge the proposal with respect to the reliability of the results for guarantying the ulterior fullment of specications.

of Institutions (State Agencies, OPIs, Technological Centres, CEM, etc.) should not prevent their coordination searching for reaching national objectives.
Industry should make an eort to understand

and integrate metrology in the productive processes, in order to get traceability, more accurate and reliable results and homogeneous devices and products. must participate in the standardization process. It is the only way of maintaining updated on the coming standards aecting their productive sectors and also them to contribute to the standards and technical specications under development, modifying these to align to their productive processes. Ministries and stakeholders (producers, users, technology developers, researchers, social agents, consumer organizations, etc.) asking for increasing the participation of members and experts in the GET 15 Committee Standardization on nanotechnologies and through this, into CEN and ISO Committees. It is crucial to build and defend a solid national position in the process of developing written standards and technical specications, before these being mandatory in Spain.

Industry

Standardization is also a reliable and ecient

tool to accelerate the dissemination of R&D results to the market. Consequently, it is necessary to promote the incorporation of a standardization component in R&D projects, and to establish the required communication channels between R&D projects and AENORs AEN/GET 15 Committee Nanotechnologies to foster the development of standards and guidelines that contribute to provide the necessary tools to producers and condence to users and consumers.

AENOR should make a call to the concerned

Increase the support and funding of

metrological infrastructures able to produce primary standards, measurement services and technical expertise, as required by edge technology and measurements at the nanoscale 10 after agreement of the involved Ministries. strategic coordinated projects, with participation of Public and Private Sectors, but covering wider multidisciplinary aspects of nanotechnology and, as much as possible, metrology and standardization. technicians and post-Docs) for increasing the participation of CEM and their Associated Laboratories into the EMRP Programme, by the way of Article 169 of the European Treaty. of national and regional coordinated activities of Knowledge Transfer to disseminate the metrological principia and criteria to Academia, Research Community and Industry. The existence of dierent type
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Maintaining the launching of singular and

5. Infrastructure needed to meet objectives within the period 2010-2013

Existing infrastructure based on Technological

Support of MITYC (funding and recruitment of

Platforms, Networks, Universities, SMEs, etc., is valid and should be maintained but increasing the dissemination of knowledge and the coordination of actions, mainly when the actors belong to dierent Ministries and Institutions, as it is the case.

Organization

6. Initiatives The Spanish Centre of Metrology (CEM) (www.cem.es). Embedded in the structure of

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MITYC, among their missions are: keeping, maintaining and disseminate the national standards of the SI Units, to provide traceability to the society (calibration and test laboratories, industry, etc.), executing R&D projects on metrology, training specialists in metrology and representing Spain in front of international metrology organizations. AENOR/GET 15: Spanish Standardization Group on Nanotechnologies Structurally divided into 4 Working Groups: Terminology and Nomenclature, Measurement and Characterization, Health, Safety and Environment, Materials Characterization, it is the mirror Group of ISO/TC 229 and CEN/TC 352 Standardization on nanotechnologies and IEC/TC 113 Nanotechnology Standardization in electric and electronic equipment. Doctorate and Masters on metrology: Master on Metrology by the Spanish Centre of Metrology (CEM) and the Polytechnic University of Madrid (UPM), 2 years, 60 ECTS credits. Thematic Units: Foundations of Metrology, Physics, Statistics, Models for measurements and calibrations, Organization and Management of Metrology, Legal Metrology, Length Metrology, Temperature, Mass and derived quantities, Electrical Metrology, Chemical Metrology, Other metrologies. Integral Doctorates are less frequent although there are some. These are of general type, not specically oriented to nanotechnology. Some of them are:
Metrology and Industrial Quality, UNED -

There are also Courses on calibration and estimation of uncertainties, together with programmed subjects in technical careers, mainly in Engineering and Physics. In Europe there is a great variety of initiatives and platforms, with origin in the European Commission (EMRP and others), in National Metrology Institute Networks (EURAMET) and in Private Companies, Research Centres and Technical Universities. The main initiative related to nanometrology is Co-Nanomet, a programme of activities funded under the 7th Framework Programme of the European Commission, addressing the need within Europe to develop the required measurement frame to successfully support the development and economic exploitation of nanotechnology. Co-Nanomet's activities focus on the nanometrology needs of European Industry and are addressed through 4 key actions: Strategy denition, Action Groups (Engineered Nanoparticles, Nanobiotechnology, Thin Films and Structured Surfaces, Critical Dimensions and Scanning Probe Techniques, Modelling and Simulation), Coordination of Education & Skill and Exploitation & Development of Infrastructures. With respect to standardization and activities related to Environment, Health and Safety (EHS), the main Organizations involved are:
CEN, European Committee for Standardization

National University of Distance Education. Zaragoza University.

Design and Fabrication Engineering, UNIZAR Doctorate on Metrology, ETSII Polytechnic

(www.cen.eu), with the following Committees involved in nanotechnology: CEN/TC 137 Assessment of workplace exposure to chemical and biological agents, CEN/TC 352 Nanotechnologies, IEC/TC 113 Nanotechnologies standardization for electrical and electronic products and systems. Organisation for Economic Cooperation and Development (www.oecd.org).

Univ., Madrid, Dept. of Applied Physics.

OECD,

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JRC,

Joint Research Centre, European Commission (www.jrc.ec.europa.eu). Materials and Standards (www.vamas.org). Organisation for Standardisation (www.ecostandard.org).

VAMAS, Versailles Project on Advanced ECOS, European Environmental Citizens

7. Conclusions A lot of eort has been made in the last years in Spain to reduce the delay with respect to other European countries. The level of knowledge, development and involvement in R&D projects has grown and also the results and the rate of return of investments. But still remains a lack of information and coordination between all interested parties working in nanotechnology. Also, some matters as metrology and standardization are not suciently considered in the projects and industrial applications. So, a bigger dissemination of the knowledge among all interested parties is needed together with a coordination of eorts. It is crucial the creation of a Spanish Observatory on Nanotechnology to support Spanish decision-makers with information and analysis on developments in nanoscience and nanotechnology, coordinate all existing information, facilitate the strategic decisions of the Administration and to involve companies and society in the projects on which it is necessary to focus the attention in the coming years. In such Observatory, all interested parties (Technological Platforms, Networks, the High Council on Metrology, AENOR GET 15 Committee, etc.) must be represented. Discussions should also include metrological,

toxicological and standardization aspects of the nanotechnology, and not only those specically scientic or technological. Collaboration CEM - Academia - Industry should be enhanced as a way to detect measurement and characterization problems and needs as a previous step to invest on designing and manufacturing of metrological measurement instruments and standards, traceable and accurate, as an answer to such needs. Creation and funding of some infrastructure for CEM, their Associated Laboratories and AENOR to disseminate the knowledge on last developments in metrology and standardization at the nanoscale, for the benet of all Spanish stakeholders. Establishing and funding of Educational Programmes to improve capabilities of Universities and companies by creating multidisciplinary communities involved in research on nanotechnology and metrology applied to the nanoscale. The next conclusions have been adapted from a recent Report on Nanotechnologies and Food 11, but we see applicable to the Spanish situation too: Government should take steps to ensure the establishment of research collaborations between industry, academia and other relevant bodies at the pre-competitive stage in order to promote the translation of basic research into commercially viable applications of nanotechnologies. Government should work more closely with other EU Member States on research related to the health and safety risks of nanomaterials to ensure that knowledge gaps are quickly lled without duplication of eort, while continuing to support coordinated research in this area at an international level through appropriate international organisations including the International Organization for Standardization and Organisation for Economic Cooperation and Development.

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Government should establish an open discussion group to discuss on the application of nanotechnologies in the dierent sectors, including food. This group should contain representatives from Government, academia and industry, as well as representative groups from the public such as consumer groups and non-governmental organisations. References
1

assessment of products of nanotechnologies, 19 January 2009, pp 15-16. The European Metrology Research Programme (EMRP) is a metrology-focused European programme of coordinated R&D facilitating a closer integration of national research programmes and ensuring the collaboration between National Measurement Institutes, reducing duplication and increasing impact.
9 8

Definition 2.1, ISO TS 27687:2008, Nanotechnologies Terminology and definitions for nano-objects Nanoparticle, nanofibre and nanoplate, 1st ed., 15-08-2008.

Royal Commission on Environmental Pollution (RCEP), UK, Novel Materials in the Environment: The case of nanotechnology, p 64, Nov. 2008. Australian Government, National Measurement Institute, Technical Report 12, Nanometrology: The Critical Role of Measurement in Supporting Australian Nanotechnology, Dr John Miles, First edition, November 2006.
11 10

Nanoscale Metrology, Editorial, Meas. Sci. Technol. 18 (2007).

3

Scanning Probe Microscopy, Scanning Electron Microscopy and Critical Dimension: Nanometrology: Status and Future Needs within Europe, European Nanometrology Discussion Papers, Co-Nanomet, November 2009.

House of Lords, Session 8th January 10, Science and Technology Committee, First Report on Nanotechnologies and Food.

The National Nanotechnology Initiative: Research and Development Leading to a Revolution in Technology and Industry (2006) Subcommittee on Nanoscale Science, Engineering and Technology, Committee on Technology, National Science and Technology Council (www.nano.gov/NNI_07Budget.pdf).
5

Eighth Nanoforum Report on Nanometrology, Julio 2006 (www.nanoforum.org).

6

Towards a European Strategy for Nanotechnology (2004) European Commission, Brussels (ftp://ftp.cordis.europa.eu/pub/ nanotechnology/docs/nano_com_en.pdf).

SCENIHR (Scientific Committee on Emerging and Newly Identified Health Risks), Risk

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ADDENDUM LIST OF STANDARDS AND TECHNICAL SPECIFICATIONS UNDER DEVELOPMENT WITHIN ISO/TC 229
ISO/WD TS 10797, Nanotubes - Use of transmission electron microscopy (TEM) in walled carbon nanotubes (SWCNTs). ISO/CD TS 10798, Nanotubes - Scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDXA) in the characterization of single walled carbon nanotubes (SWCNTs). ISO/DIS 10801, Nanotechnologies - Generation of metal nanoparticles for inhalation toxicity testing using the evaporation/condensation method. ISO/DIS 10808, Nanotechnologies Characterization of nanoparticles in inhalation exposure chambers for inhalation toxicity testing. ISO/AWI TS 10812, Nanotechnologies - Use of Raman spectroscopy in the characterization of single-walled carbon nanotubes (SWCNTs). ISO/CD TS 10867, Nanotubes - Use of NIRPhotoluminescence (NIR-PL) Spectroscopy in the characterization of single-walled carbon nanotubes (SWCNTs). ISO/CD TS 10868, Nanotubes - Use of UV-Vis-NIR absorption spectroscopy in the characterization of single-walled carbon nanotubes (SWCNTs). ISO/CD TR 10929, Measurement methods for the characterization of multi-walled carbon nanotubes (MWCNTs). ISO/CD TS 11251, Nanotechnologies - Use of evolved gas analysis-gas chromatograph mass spectrometry (EGA-GCMS) in the characterization of single-walled carbon nanotubes (SWCNTs). ISO/CD TS 11308, Nanotechnologies - Use of thermo gravimetric analysis (TGA) in the purity evaluation of single-walled carbon nanotubes (SWCNT). ISO/CD TR 11360, Outline of a Method for Nanomaterial Classication. ISO/AWI TR 11808, Nanotechnologies - Guidance on nanoparticle measurement methods and their limitations. ISO/NP TR 11811, Nanotechnologies - Guidance on methods for nanotribology measurements. ISO/CD TS 11888, Determination of mesoscopic shape factors of multiwalled carbon nanotubes (MWCNTs). ISO/AWI TS 11931-1, Nanotechnologies - Nanocalcium carbonate - Part 1: Characteristics and measurement methods. ISO/NP TS 11931-2, Nanotechnologies - Nanocalcium carbonate - Part 2: Specications in selected application areas. ISO/AWI TS 11937-1, Nanotechnologies - Nanotitanium dioxide - Part 1: Characteristics and measurement methods. ISO/NP TS 11937-2, Nanotechnologies - Nanotitanium dioxide - Part 2: Specications in selected application areas. ISO/CD 12025, Nanomaterials - General framework for determining nanoparticle content in nanomaterials by generation of aerosols.

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ISO/CD TR 12802, Nanotechnologies Terminology - Initial framework model for core concepts. ISO/AWI TS 12805, Nanomaterials - Guidance on specifying nanomaterials. ISO/AWI TS 12901-1, Nanotechnologies Guidance on safe handling and disposal of manufactured nanomaterials. ISO/NP TS 12901-2, Guidelines for occupational risk management applied to engineered nanomaterials based on a "control banding approach". ISO/AWI TR 13014, Nanotechnologies - Guidance on physico-chemical characterization of engineered nanoscale materials for toxicologic assessment. ISO/AWI TR 13121, Nanotechnologies Nanomaterial Risk Evaluation Framework. ISO/NP TS 13126, Articial gratings used in nanotechnology - Description and measurement of dimensional quality parameters. ISO/NP TS 13278, Carbon nanotubes Determination of metal impurities in carbon nanotubes (CNTs) using inductively coupled plasma-mass spectroscopy (ICP-MS). ISO/NP TR 13329, Nanomaterials - Preparation of Material Safety Data Sheet (MSDS). ISO/DIS 29701, Nanotechnologies - Endotoxin test on nanomaterial samples for in vitro systems - Limulus amebocyte lysate (LAL) test. ISO/AWI TS 80004-1, Nanotechnologies Vocabulary - Part 1: Core terms.

ISO/CD TS 80004-3, Nanotechnologies Vocabulary - Part 3: Carbon nano-objects. ISO/AWI TS 80004-4, Nanotechnologies Vocabulary - Part 4: Nanostructured materials. ISO/AWI TS 80004-5, Nanotechnologies Vocabulary - Part 5: Bio/nano interface. ISO/AWI 80004-6, Nanotechnologies - Vocabulary - Part 6: Nanoscale measurement and instrumentation. ISO/AWI TS 80004-7, Nanotechnologies Vocabulary - Part 7: Medical, health and personal care applications. ISO/NP TS 80004-8, Nanotechnologies Vocabulary - Part 8: Nanomanufacturing processes.

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> NIEK VAN HULST Place and date of birth Nijmegen (The Netherlands), 1957 Education Study: Astronomy and Physics, at University of Nijmegen, the Netherlands. PhD: in molecular physics, at University of Nijmegen, the Netherlands. Experience Senior group leader Molecular NanoPhotonics, ICFO The Institute of Photonic Sciences, Castelldefels - Barcelona, Spain. ICREA research professor, ICREA - Catalan Institute for Research and Advanced education, Barcelona, Spain. Full Professor Nano-Optics, MESA+ group leader, Dept. Science & Technology, MESA+ Institute for Nano-Technology, the Netherlands Assistant Professor, Applied Optics group, University of Twente, the Netherlands Lecturer/Researcher, Applied Optics group, University of Twente, the Netherlands Postdoctoral Researcher, Opto-Electronics, (Technical) University of Twente, the Netherlands Niek van Hulst has a background in molecular physics, non-linear optics, scanning probe microscopy and nanophotonics. He develops advanced optical nano-antennas, for applications both in chemistry and biology and in advanced integrated optical devices. His group developed the technique of optical phase mapping and pulse tracking which lead to the rst direct observation of slow light in photonic crystals. Also the group demonstrated the rst /4 monopole optical antenna probe with <20 nm eld localization. Current activities are on the control of single quantum systems by phase shape pulses and dedicated optical antennas. Niek van Hulst is coordinator of the Spanish Consolider program NanoLight.es. niek.vanhulst@icfo.es

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1. Introduction Photonics - the scientic study and application of light - has evolved to become a key technology behind many devices found in the modern home, factory and research lab. Today, photonics is a multibillion-dollar industry, underpinning applications such as telecommunications, data storage, at-panel displays and materials processing. Nanometer scale optical architectures play an essential role in future dense optical circuits, optical data storage and materials chemistry. To this end both nanostructured (top-down) and colloidal (bottom-up) architectures are pursued in parallel. Indeed the optical response of nanostructures exhibits fascinating new entries: subwavelength spatial variation of the eld, enabling nanoscale imaging; strong local eld enhancement with respect to the incident wave, allowing nanoscale lasing, trapping and heating; local elds with polarization, magnetic and spatial components that are not present in the incident light; extraordinary transmission, negative index and negative refraction, sparking o the new eld of optical metamaterials. All these phenomena are important for applications in the area of nanophotonic circuits [4, 5], biology, medicine and environmental energy issues. For example, the sub-wavelength variation is exploited for nanoscale optical circuits and for nanoantennas that enable high spatial resolution in imaging and sensing. Moreover, the

combination with ultrafast laser spectroscopy opens many possibilities for light control and nonlinear ultrafast optics, all on the nanoscale. Throughout the past decade NanoPhotonics research in Spain has build-up a strong international reputation. Particularly research on photonic crystals was initiated early, while the understanding of the physics behind extraordinary transmission in metallic nanostructures has been largely driven by Spanish theory. More recently research in plasmonics and metamaterials is growing rapidly and being recognized internationally. While based on a traditionally and continuously strong position in theory, it is interesting to see how several new experimental institutes and research groups with high scientic prole and ample nano-facilities for NanoPhotonics are getting shape (Barcelona, San Sebastian and Valencia). The new initiatives often nd their origin in the comunidades (Antonomous Regions), while being strengthened by national mechanisms, such as the Plan Nacional and especially the CONSOLIDER program. Future perspective for Spanish NanoPhotonics is denitely positive on the short term, however the horizon beyond 2 or 3 years remains unclear, also due to recent cuts in research budget. 2. State of the art NanoPhotonics is currently a very active and competitive research eld with rapid

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developments. The current state-of-the-art of nanofabrication allows to fabricate new generations of optical nanostructures, (meta)materials and optical antennas, with new properties by proper engineering of the electromagnetic elds on the nanometre scale. At the same time a broad range of applications is opened up ranging from quantum-information to light harvesting and energy conversion to biosensing and optical imaging with nanometric resolution. Here developments in a selection of NanoPhotonics topic are sketched: 2.1 Metamaterials Novel electro-magnetic properties, such as a negative refractive index, can be achieved by clever engineering of articial composite (meta)materials, building on sub-wavelength structures. The new properties are not attainable with naturally occurring bulk materials. Functional negative-index metamaterials were rst demonstrated for microwave frequencies, immediately opening the search for analogous materials at optical frequencies. Indeed rst principle of optical negative refraction and super-lensing were demonstrated using thin metal lms, however challenging fabrication of nanometrically at lms and the enormous energy dissipation in metals are an obstacle for practical application. Novel strategies combining nanocontrolled metallic and dielectric structures are required to optimize between negative permittivity and the concomitant losses. Interest has turned to threedimensional optical metamaterials, based on layered semiconductor metamaterials or magnetic metamaterials in the infrared frequencies, indeed showing negative refraction. Recently relatively low-loss metamaterial have been presented, based on the so-called of cascaded shnet structures, possessing a negative index over a broad spectral range, and accessibility from free space. Clearly the novel design of negative index metamaterials is challenging both from the theoretical and nanofabrication point-of-view. If successful a

completely new arena of controlling light at the nanoscale comes at hand. To date the research eld is very active, as negative and zero-index meta-materials oer unique prospects for superlensing, optical tunnelling devices, compact resonators and highly directional sources, etc. 2.2 Plasmonic nanolasers Truly nanometre-scale lasers has long been one of the main goals of nanophotonics research. Despite early theory on the concept of surface plasmon lasers, so-called Spasers, ohmic losses at optical frequencies have long inhibited the realization of plasmonic nanolasers. Hybrid plasmonic-photonic waveguides allow to reduce signicantly the losses while maintaining ultrasmall modes. Indeed recently the rst experimental demonstration of nanometre-scale plasmonic lasers was reported using a nanowire separated from a metallic surface by a nm-scale insulating gap, generating optical modes a hundred times smaller than the diraction limit. The plasmonic modes have no cut-o, therefore the dimensions can be even further down-scaled. Plasmonic lasers thus oer the possibility of exploring extreme interactions between light and matter, opening up new avenues in the elds of active photonic circuits, bio-sensing and quantum information technology. 2.3 Optical Antennas Antennas play a key role in our modern wireless society, as they mediate between free electromagnetic waves and electronic circuitry, thus enabling mobile phone, internet, etc. Only in recent years the crucial role of nano-optical antennas as a transducer between the high frequency (~500 THz) optical near and far eld was realized. In fact the extensive library of antenna shapes and sizes, optimized to increase the amount of radiated power for a given frequency band and specic emission direction, can be scaled down to the optical regime for nanoscale optics. However there is no simple downscaling, as the physics of nanoantennas is

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2.5 Imaging and sensing In recent years nanoscopy optical microscopy with 10-30 nm detail, has become a reality. By proper engineering of the microscopical point spread function, in combination with non-linear response, the eective resolution is now an order of magnitude below the diraction limit. Particularly STimulated Emission Depletion (STED) microscopy has moved into active applications, mainly in biology. In parallel the controlled photo activation of single molecules has allowed the concept of Photo-Activation Localisation Microscopy (PALM), with eective resolution reaching the 20 nm, a method nding applications extremely rapidly. At the same time strong attention is on resonant metallic particles that enhance the local eld enhancement and on nano-antenna congurations which aord improved coupling eciency. Several types of antenna geometries are being pioneered for nanoscaling imaging in biology and technical application, again with resolution in the 20 nm range. In parallel, new physics routes are explored through superlensing by negative index (meta)materials, where the evanescent decay is locally inverted to gain; unfortunately, material losses are competing heavily with the superlensing eciency. 2.6 Nanophotonic manipulation Small particles can be trapped by optical elds, the so-called optical tweezers. The near eld photonic forces generated at nanostructures or arrays of nanoholes provide a novel route of control, to trap nanoparticles in nanochannels,

Nano-optical antennas oer unique new opportunities. They do allow conning and controlling optical elds truly on the nanometer scale. Even more, in close proximity to photon emitters, such as molecules, Q-dots or color centers, nano-antennas are particularly promising. First, they boost the radiative rate far over intrinsic non-radiative decay, thus with the potential to generate super-emitters with ps photo-cycling times. Indeed 100-fold lifetime reduction to 10 ps regime was reported recently. Second, nanoantennas funnel the incident far eld eciently to dedicated antenna mode maxima thus nanofocusing the incident light on e.g. a Q-dot. Last, not least, antennas redirect all photon emission in a dedicated direction with narrow angle. Indeed complete redirection of radiation patterns over 90 degrees was reported recently. 2.4 Phase control of nanoscale optical elds By exploiting the interplay between the nanostructure and the spatio-temporal light eld a high degree of control is attainable. Size and shape of the nanostructure play a vital role. For example theoretical modelling has shown that the eld distribution of a tapered nanostructure depends directly on the linear chirp of a femtosecond excitation pulse. Thus the light is slowed down and ultimately stopped or trapped. Recently rst results were reported that shaping allows specic control over the spatio-temporal nanoscopic eld. Thus, pulse sequences can be generated in which local excitations occur at specic time and position with sub-diraction resolution.

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much richer. First, one has to take into account the plasmonic properties of metals at optical frequency. Second, nanoscale optical sources are atoms, organic molecules or semiconductor quantum dots (Q-dots), i.e. quantum systems; therefore one enters the quantum regime of single photon emitters. Finally optical nanoantennas are truly small, with dimensions between 30 and 500 nm, posing challenges both to fabrication and novel methods to drive and tune such antennas.

This opens the route towards space-time-resolved spectroscopy with direct observation of nanoscopic energy transport. The challenge lies in the optimization of a number of near-eld observables, exploiting properly shaped laser pulses, to achieve ultimate spatial control over linear and nonlinear electromagnetic ux, the local spectrum, and the local temporal intensity prole.

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in direct competition with Brownian motion, to develop extremely sensitive sensors for detecting the binding of (bio)molecules to the particles. Control and understanding of the conditions for the ecient trapping of the nanoparticles in the near eld of such nanoholes, requires detailed insight in the light interactions between the nanoparticles and the hole walls. Once mastered, the detection of the binding of a single molecule to a trapped particle could be realized, through enhanced surface Raman scattering by particle plasmon resonances. Moreover for extraordinary optical transmission, the extreme eld concentrations close to the hole will have dramatic eects on the strength of these forces that broaden the range of applications. Indeed successful nanoscale optical trapping on both resonant nanoparticles and nanoholes has been reported, while applications are being explored. Metallic nanoparticles are generally lossy. Thus, besides forces, the resonantly driven nanostructures will heat up. Here the losses can be used into advantage for dedicated nanoscale heating. When used in combination with proper biochemical recognition methods one can envision localized heating and even destruction of selected biomaterial. Indeed plasmonic heating therapies are currently passing through the clinical test phase. 2.7 Nanophotonics for energy In traditional solar cells photovoltaics is to use light for generating charge carriers in a semiconductor, where the spatial separation of the charge carriers denes a current in an external circuit. For maximum eciency it is important to absorb most of the incoming radiation. Plasmonic nanoparticles have large optical cross-sections and can eciently collect and scatter photons into the far eld. Thus rst an increased eective optical path length and greater photon absorption probability are achieved. Secondly, the spatially localized near eld photons created in the immediate vicinity

of plasmonic particle can directly excite electronhole pairs in an indirect gap semiconductor even without phonon assistance, increasing light absorption per unit thickness. Finally charge-carrier can be injected directly from the nanoparticle into the semiconductor. Nanoparticle assisted solar cells are currently a very active research subject. 3. International publications R. F. Oulton , V. J. Sorger, T. Zentgraf, R. M.Ma, C. Gladden, L. Dai, G. Bartal , X. Zhang. Plasmon lasers at deep subwavelength scale. Nature Vol. 461, Issue: 7264, 629-632, Published: Oct 1 2009. J. Valentine, S. Zhang, T. Zentgraf, E. Ulin-Avila, D. A. Genov, G. Bartal and X. Zhang. Three Dimensional Optical Metamaterial Exhibiting Negative Refractive Index. Nature, Vol. 455, 376, 2008. M. A. Noginov, G. Zhu , A. M. Belgrave , R. Bakker, V. M. Shalaev, E. E. Narimanov, S. Stout, E. Herz, T. Suteewong, U. Wiesner. Demonstration of a spaser-based nanolaser. NATURE Vol. 460, Issue: 7259, 1110-U68, Published: Aug 27, 2009. S. Lal, S. E. Clare, N. J. Halas. Nanoshell-Enabled Photothermal Cancer Therapy: Impending Clinical Impact. Accounts of Chemical Reserarch, Vol. 41, Issue: 12, 1842-1851, Published: Dec 2008. S. Noda, M. Fujita, T. Asano. Spontaneous-emission control by photonic crystals and nanocavities. Nature Photonics, Vol. 1, Issue: 8, 449-458, Published: Aug 2007, Times Cited: 90. H. J. Lezec, J. A. Dionne, H. A. Atwater. Negative refraction at visible frequencies. Science, Vol. 316, Issue: 5823, 430-432, Published: Apr 20, 2007.

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T. H. Taminiau, F. D. Stefani, F. B. Segerink, N. F. Van Hulst. Optical antennas direct single-molecule emission. Nature Photonics, Vol. 2, Issue: 4, 234-237, Published: Apr, 2008. T. Baba. Slow light in photonic crystals. Nature Photonics, Vol. 2, Issue: 8, 465-473, Published: Aug, 2008. L. Novotny. Eective wavelength scaling for optical antennas. Physical Review Letters, Vol.98, Issue: 26, Article Number: 266802, Published: Jun 29, 2007. N. I. Zheludev, S. L. Prosvirnin, N. Papasimakis, V. A. Fedotov. Lasing spaser. Nature Photonics, Vol. 2, Issue: 6, 351-354, Published: Jun, 2008. A. Alu, N. Engheta. Tuning the scattering response of optical nanoantennas with nanocircuit loads. Nature Photonics, Vol. 2, Issue: 5, 307-310, Published: May, 2008. T. V. Teperik, F. J. Garca De Abajo, A. G. Borisov, M. Abdelsalam, P. N. Bartlett, Y. Sugawara & J. J. Baumberg. Omnidirectional absorption in nanostructured metal surfaces. Nature Photonics 2, 299 - 301 (2008). M. Righini, P. Ghenuche, S. Cherukulappurath, V. Myroshnychenko, F. J. Garca de Abajo, R. Quidant.

E.Rittweger, K. Y. Han, S. E. Irvine, C. Eggeling, S. W. Hell. STED microscopy reveals crystal colour centres with nanometric resolution. Nature Photonics, Vol. 3, Issue: 3, 144-147 Published: Mar, 2009. A. Kinkhabwala, Z. F. Yu, S. H. Fan, Y. Avlasevich, K. Mullen, W. E. Moerner. Large single-molecule uorescence enhancements produced by a bowtie nanoantenna. Nature Photonics, Vol. 3, Issue: 11, 654-657 Published: Nov, 2009. M. Schnell, A. Garca-Etxarri, A. J. Huber, K. Crozier, J. Aizpurua, R. Hillenbrand. Controlling the near-eld oscillations of loaded plasmonic nanoantennas. Nature Photonics, Vol. 3, Issue: 5, 287-291, Published: May 2009. Stockman M. I. Criterion for negative refraction with low optical losses from a fundamental principle of causality. Physical Review Letters, Vol. 98, Issue: 17, Article number: 177404, Published: Apr 27, 2007. 4. Actions to be developed in Spain Focus and mass: NanoScience and Technology is rather scattered in Spain. Many nano-centers do exist or are in planning, where typically every Autonomous Region will have its own nanocenter, while Madrid, Catalunya, Basque country have multiple nanocentres. It is essential to refocus this trend from quantity towards quality. A dierentiation is needed to ght the fragmentation and to justify the large number of

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M. Burresi, D. Van Oosten, T. Kampfrath, H. Schoenmaker, R. Heideman, A. Leinse, L. Kuipers. Probing the Magnetic Field of Light at Optical Frequencies. Science, Vol. 326, Issue: 5952, 550-553, Published: Oct 23, 2009.

Nano-optical trapping of Rayleigh particles and Escherichia coli bacteria with resonant optical antennas. Nano Letters 9, 3387-3391 (2009).

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centres: each centre should focus on a wellchosen specialism, thus proving its uniqueness and quality. Only this way focus, critical mass and collaboration can be guaranteed. For the specic case of NanoPhotonics, concentrated research activities at 2 or 3 centres would be sucient to keep focus and critical weight. Platform: NanoPhotonics is an active research eld in Spain, carried by a large variety of institutions, foundations, and research programs. Researchers meet regularly on various types of conferences, schools and progress meetings. The exchange of information and level of collaboration is quite satisfactory but has room for further improvement. It will be useful to study the added value and necessity of a national platform for NanoPhotonics Funding: Nanophotonics research is nanced through Plan Nacional, through CONSOLIDER programs and complemented by European projects. Long term structural nancing is lacking and the horizon beyond 2011 remains unclear. Therefore it is paramount to launch a nanoscience research funding platform, with a clear focus on the various most promising and tactical nano-research directions. Herein NanoPhotonics should be one of the focus areas. Knowledge and Technology Transfer: Finally of course it is essential to stimulate actively connections between nanotechnology research and the various types of industrial activities, to promote spin-o companies, joint ventures and increase awareness of intellectual property. 5. Necessary infrastructure to achieve objectives NanoPhotonics research relies on two types of infrastructure: nanofabrication and advanced optical methods. For the nanofabrication are essential: UV-lithography, e-beam lithography, ion-beam milling, thin lm depositions, dedicated etching, electron microscopy, atomic force microscopy, near eld microscopy, surface chemistry and colloidal chemistry. Thus in practice a well-equipped clean room is

necessary for a nanophotonics laboratory. In parallel a wide range of sensitive optical methodologies is essential: broad band spectroscopy, confocal microscopy, near eld microscopy, single molecule/quantum-dot detection, non-linear optics, ultrafast excitation/detection, etc.

Figure 1. Paired nanowires make robust plasmotic waveguides.

6. Existing initiatives In the European 7th framework Photonics is one of the topics with special attention, in view of its importance for European industry and to safeguard the European photonic strength in competition with Asia and United States. In 2005 Photonics21 (www.photonics21.org), a European Technology Platform, was founded aiming at coordinating education, research, training, and development activities in the eld of photonics in Europe. Currently, it has over 1400 stakeholders from 49 countries. Fotnica21 (www.fotonica21.org) is the analogue Spanish Photonics Technology Platform. EPIC, the European Photonics Industry Consortium, is working with industries, universities, and the European Commission to build a more competitive photonics industrial

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Spanish NanoPhotonics research is strong in Europe. Already in 6th Frame work Spanish groups contributed substantially to Networks of Excellence PlasmoNanoDevices, PhOREMOST and MetaMorphose; and to STREP programs Pleas, Spans and PlasmoCom. In Framework 7 Spain coordinates the NoE NanoPhotonics for Energy Eciency (Gonal Badenes, ICFO) and STREP program SPEDOC (Romain Quidant, ICFO). The European Integrated Activity, LaserLab-Europe has expanded in the 7th Framework with the inclusion of Spanish laboratories: CLPUSalamanca and ICFO-Barcelona. The European Science Foundation (ESF) program Plasmon-BioNanoSense, with 6 Spanish groups and coordination by Stefan Maier (Imperial College, London) and Niek van Hulst (ICFO Barcelona). The network provides the means and resources for Spain to play a leading and guiding role in the future European research agenda in plasmonics, nanophotonics and biosensing; all elds of strong activity and immediate importance for industrial applications. Nationally the CONSOLIDER program NanoLight aims at developing nanoscale light

A rst Spanish conference on NanoPhotonics, CEN2008 Conf. Espaola de Nanofotnica was organized in Tarragona 2-4 April 2008; in June 2010 a 2nd meeting CEN2010 took place in Segovia. Finally NanoPhotonics is one of the focus areas of the platform NanoSpain as managed by the Phantoms Foundation. Both the national annual NanoSpain conference and the international TNT (Trends in NanoTechnology) conference series have dedicated NanoPhotonics sessions. 7. Conclusions NanoPhotonics is a very active research eld opening several new horizons, such as controlled single photon sources for quantum-information; light harvesting; energy conversion; ecient biosensors; optical imaging with 10 nm resolution. The Spanish role in international NanoPhotonics research is currently quite strong and it will be important to consolidate or improve this position towards the future. For future actions it is important to keep scientic focus and mass, to guarantee long term funding and to enforce the connection with industry.

Figure 2. NanoParticles trapping with resonant optical antennas.

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sector. In parallel the NanoPhotonics Association Europe (www.nanophotonics europe.org), was initiated (coordinated by ICFO Barcelona), involving the major European research centres, to create a common voice for NanoPhotonics particularly.

technology for applications in sensing, nanoimaging, optical circuitry and data storage. ICFO group leader Niek van Hulst is coordinator of the NanoLight project, which involves ICFO, several CSIC, institutes in Madrid, Valencia, Zaragoza, and groups at the Autonomous University of Madrid. The NanoLight Scientic Advisory Board has members from England, France, Germany, Italy, the Netherlands and the USA. In parallel the CONSOLIDER-program MetaMaterials aims at design realization and application of MetaMaterials both at microwave and optical frequencies. Javier Marti, director of the NanoPhotonic Technology Center at the Politechnical University of Valencia coordinates the MetaMaterials program.

> RICARDO GARCA Place and date of birth Len (Spain), 1960 Academic career Professor of Scientic Research, CSIC. Research Scientist, CSIC. Tenure Scientist, CSIC. Research Associate at the Instituto de Microelectrnica de Madrid (CSIC). Post-doctoral associate, University of Oregon (USA). Post doctoral fellow, University of New Mexico (USA). PhD in Physics, Universidad Autnoma de Madrid (Spain) . Master in Physics, Universidad de Valladolid (Spain). Experience Garca applies a combined theoretical and experimental approach to develop multipurpose tools for quantitative analysis and manipulation of molecules, materials and devices in the 1 to 100 nm length scale. A key feature of RGs approach is that nanoscale control and device performance should be compatible with operation in technological relevant environments (air or liquids). He has contributed to the emergence and optimization of a versatile nanolithography for the fabrication of nano-scale devices based on the spatial connement of chemical reactions (local chemical nanolithography). He has also contributed to the development, understanding and optimization of amplitude modulation AFM (tapping mode AFM). In particular, he participates in the development of multifrequency AFM as a unifying scheme for topography and quantitative mapping of material properties with sub-1 nm resolution. ricardo.garcia@imm.cnm.csic.es

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1. Introduction In the eighties research on scanning tunneling microscopy (STM) was at its apogee. A Spanish institution, the Universidad Autnoma de Madrid was at the forefront of the STM activity. This early start in the development of one of the instruments that epitomizes the emergence of nanoscience was the result of the continuous eort of several professors, scientists and graduate students. In particular, credit must be given to the vision and perseverance of Nicols Garca, Arturo Bar and Fernando Flores. Since then, two generations of Spanish scientists have kept an internationally competitive level. In some topics, it could be argued that Spains leads the way. This claim is supported by the number, impact and quality of the contributions that are originated from Spains scientic institutions. But it can also be gauged by the fact that in the period covered by this report (2007-2009), three major conferences on SPM has been held in Spain. Barcelona hosted the 1st AFMBioMed conference with about 200 participants. Then, Madrid hosted the two major international conferences on atomic force microscopy (the 11th Non Contact, Madrid 16-19 September 2008; 11th International Scanning Probe Microscopy, Madrid 17-19, June 2009). About 200 scientists attended each conference. The scientic board of both conferences has members based on Spain.

In addition, Madrid has hosted the rst two conferences on Multifrequency AFM (15th September 2008, 15-16 June 2009).

Figure 1. Scheme of the cantilever oscillation in bimodal AFM (R.G.)

An estimation of the size of Spains SPM community can be obtained from the number of participants in the Spanish conference on SPM, called Fuerzas y Tnel. This is a biannual meeting that in 2008 had 109 attendees with 37 oral presentations and 45 posters. Right now there are about 25 groups that actively work on either the development of applications of probe techniques. Those groups cover almost all the range technical applications and developments. Madrid and Barcelona are the poles of this activity. Shortly, Madrids activity shows a balance among instrumentation, applications and theoretical methods. The activity in Barcelona is more oriented towards applications. These range from cell biology to materials science or microelectronics.

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A welcome event in this period has been the incorporation to some Spanish institutions of several scientists with considerable SPM expertise, notably Rainer Hillebrand, Nicols Lorente, Fernando Moreno or Esther Barrena. It has to be emphasized that the strength and vigor of the scientic activity is not the result of a concerted eort by Spanish agencies to support SPM. Mostly, it has been driven by the vision and the curiosity of some scientists. 2. State of the art The analysis is divided in three sections: atomic force microscope (AFM), STM and a brief section devoted to the theory applied to explain scanning probe microscopy experiments. 2.1 Atomic force microscopy The AFM shows an admirable vitality. Twenty years after the invention of the instrument and there is still plenty of room for innovative dynamic AFM approaches. Instrumentation. In this period there are two major milestones in AFM methods. The collaboration between Julio Gmez and Jos M. Gmez groups (UAM) gave rise to the WSxM software (1). This is a free software designed to run a wide variety of SPM congurations and that is

compatible with Windows operative system. The impact of the WSxM software has been outstanding. In a single year (2009) the publication has been cited 297 times. Another highlight was the development of bimodal AFM (2-3). This method improves the sensitivity of tapping mode AFM by 10-100 times. As a consequence, it makes compatible high resolution imaging while applying very small forces. This technique belongs to the Multifrequency AFM concepts that are one of the current poles of AFM research. San Paulo, Bachtold and colleagues (CSIC) have exploited the high sensitivity of bimodal excitation for imaging the vibration modes of several nanoelectromechanical systems such as suspendend carbon nanotubes or graphene resonators (4). Noteworthy is the collaboration established between A. Asenjo and colleagues (CSIC) and a company (Nanotec Electronica) to implement a magnetic force microscope adapted to the operation under external magnetic elds. Applications. The imaging as well as the spectroscopy capabilities of the AFM has been widely exploited to study a wide range of materials: biomolecules, nanotubes, semiconductors to name a few. It is worth to mention the pioneering attempts to manipulate the mechanical exibility of virus capsids by a team of UAM and CSIC scientists (5).

Figure 2. Image of the vibrational modes of a carbon nanotube (Courtesy A. San Paulo)

Figure 3. Section of a silicon nanowire transistor fabricated by AFM nanolithography (Courtesy R.G.)

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2.3 Theory New codes to interpret STM images have been proposed (J.M. Soler), however, the current theoretical activity is applied to explain the experimental data based on previous theoretical developments (J. Cerd, N. Lorente). The capability of the AFM to investigate the electrical and mechanical properties of nanoscale systems

2.2 Scanning tunneling microscopy The use of the STM in ultra high vacuum conditions has been crucial to determine the growth conditions of dierent nanoscale systems. Instrumentation. The most noticeable instrumental development has been the design and construction of a low temperature (4K) ultra high vacuum STM by J.M. Gmez-Rodrguez and colleagues. This instrument has been used to study dierent surface diusion studies of single molecules and nanostructures on solid surfaces. Applications. The atomic resolution of the STM has been exploited for addressing several key studies in nanoscience (9-13). Martin-Gago and colleagues have followed in-situ chemical reactions on catalytic surfaces. In particular, they have successfully synthesized both fullerene, C60, and triazafullerene, C57N3, with yields close to 100 per cent by means of a surface catalyzed dehydrogenation process from their corresponding planar polycyclic aromatic precursors (9).

Figure 4. Scheme of the synthesis of C60 (Courtesy J. A. Martin-Gago)

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The unique ability of the AFM to provide spatially resolved electrical measurements has been exploited to measure the electrical properties of dierent nanotubes (6-7). Regarding the nanofabrication potential of AFM, it is worth to mention the introduction of dip-pen nanolithography in Spain by the AFM community (D. Maspoch and D. Ruiz-Molina). The maturity of AFM oxidation as an alternative nanolithography has been illustrated by the fabrication of sub-5 nm silicon nanowire transistors (see gure). Cantilever-based nanomechanical sensing implements some AFM technology to detect with a exceedingly good sensitivity mass changes of or interactions. Javier Tamayos group (CSIC) has proposed a novel scheme to the development of a label-free DNA biosensor that can detect single mutations (8).

Gambardella and colleagues have imaged with atomic resolution supramolecular layers. The images have contributed to understand the origin of the magnetic anisotropy in twodimensional iron arrays (10). Hermann Suderow and colleagues have fully exploited the spectroscopy capabilities to image a superconducting vortex lattice (11). They reported one of the rst images of a two dimensional melting transition. In another relevant study, Vazquez and colleagues have applied the imaging and spectroscopy capabilities of the STM to characterize the formation of a periodically rippled graphene surface (13).

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has motivated an intense theoretical activity (F. Flores and colleagues, P.A. Serena). First principle calculations are extensively been used to explain the electrical and mechanical properties of nanosystems. In particular, the collaboration of R. Prez with Moritas group in Japan has produced fruitful results to explain atomic-scale manipulation experiments (14-15). The emergence of multifrequency AFM methods has prompted a theoretical framework to explain the experiments (2). Some theoretical aspects of phase imaging have also been revisited (J. J. Senz, R. Garca). 3. International Publications I. Horcas, R. Fernndez, J.M. GmezRodrguez, J. Colchero, J. Gmez-Herrero, A.M. Bar, WSxM: A software for scanning probe microscopy and a tool for nanotechnology, Review Scientic Instruments 78, 013705 (2007). J. R. Lozano, R. Garca, Theory of multifrequency AFM, Physical Review Letters 100, 076102 (2008). R. Garca, R. Magerle, R. Prez, Nanoscale compositional mapping with gentle forces, Nature Materials 6, 405 (2007). D. Garca-Snchez, A. San Paulo, M.J. Espandiu, F. Prez-Murano, L. Forr, A. Aguasca, A. Bachtold, Mechanical detection of carbn nanotube resonator vibrations, Physical Review Letters 99, 085501 (2007). C. Carrasco, M. Castellanos, P.J. de Pablo, M.G. Mateu, Manipulation of the mechanical properties of a virus by protein engineering, Proc. Natl. Acad. Sci. USA 105, 4150 (2008). B. Prez-Garca, J. Zuniga-Prez, V. MuozSnjose, J. Colchero, E. Palacios-Lidon, Formation and rupture of Schottky nanocontacts on ZnO naocolumns, Nano Letters 7, 1505 (2007).

P. Sundqvist, F. J. Garca-Vidal. F. Flores, M. Moreno-Moreno, C. Gmez-Navarro, J. S. Bunch, J. Gmez-Herrero, Voltage and lengthdependent phase diagram of the electronic transport in carbon nanotubes, Nano Letters 7, 2568 (2007). J. Merteens, C. Rogero, M. Calleja, D. Ramos, J. A. Martn-Gago, C. Briones, J. Tamayo, Labelfree detection of DNA hybridization based on hydration-induced tension in nucleic acid lms, Nature Nanotechnology 3, 301 - 307 (2008). G. Otero, G. Biddau, C. Snchez-Snchez et al. Fullerenes from aromatic precursors by surface-catalysed cyclodehydrogenation , Nature 454, 865 (2008). P. Gambardella, S. Stepanow, A. Dmtriev, J. Honolka et al., Supramolecular control of the magnetic anisotropy in two-dimensional highspin Fe arrays at a metal interface, Nature Materials 8, 189 (2009). I. Guillamon, H. Suderow, A. FernndezPacheco, J. Sese, R. Cordoba, J.M. de Teresa, M.R. Ibarra, S. Vieira, Direct observation of melting in a two-dimensional superconducting vortex lattice, Nature Physics 5, 651 (2009). I. Fernndez-Torrente, S. Monturet, K.J. Franke, J. Fraxedas, N. Lorente, J.I. Pascual, Long-range repulsive interaction between molecules on a metal surface induced by charge transfer, Physical Review Letters 99, 176103 (2007). A. L. Vzquez, F. Calleja, B. Borca, M.C.G. Passaseggi, J.J. Hinarejos, F. Guinea, R. Miranda, Periodically rippled graphene: Growth and spatially resolved electronic structure, Physical Review Letters 100, 056807 (2008). O. Custance, R. Prez, S. Morita, Atomic force microscopy as a tool for atom manipulation, Nature Nanotechnology 4, 803 (2009).

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4. Proposed actions in Spain Spains international prominence on SPM has mostly been driven by the curiosity of the scientists. This is, somehow regrettable, because the involved technologies are one of the pillars that sustain the advance on nanotechnology. SPM projects are currently funded by the main programs of the MICINN. However, those programs allocated a limited amount of funds what limits the scope of the projects. If Spain is to maintain a leadership in new generation of scanning probe microscopes, SPM projects should be present on the large scientic programs such as CONSOLIDER or other more technology oriented actions. 5. Infrastructure The prole of the scientists involved in SPM activities can be divided into three major groups: developers of SPM methods, experts that perform sophisticated measurements and users aiming nanoscale characterization. Those scientists and technologists have dierent needs and expectations from the technique. To properly address those needs and to identify potential new users, it would be helpful compile a database of the instruments devoted to each activity. 6. Other initiatives Currently, there are two master courses that give a central role to SPM techniques: Master Interuniversitario en Nanociencia y Nanotecnologa molecular (coordinated by the Universidad de Valencia) and Master en Fsica de la Materia Condensada y Nanotecnologa (coordinated by the Universidad Autnoma de Madrid). The Comunidad de Madrid supports a
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7. Conclusion In the reporting period, some signicant advances in scanning probe microscopy instrumentation and applications have happened in. The SPM activity shows scientic vitality, strength and growth. It can be said that history of the SPM activity is a history of a double success. First, because an activity that started about 25 years ago has kept a very high scientic prole. Second, for the rst time in modern Spanish science, a scientic activity has kept an internationally competitive level in the three major aspects: instrumentation, applications and theory. In fact, this success is the result of several factors such as the vision of the pioneers, the existence of a sizeable group of experts that cover all topics from instrumentation to theory and the nancial support by the Spanish funding agencies. If the next evolution in nanoscale instrumentation is not to be missed, the funding agencies should consider the opportunity to stimulate and fund a large collaborative project in this eld. To some extent, it is odd that the Consolider-Ingenio 2010 program does not included a project specically devoted to novel scanning probe microscopy methods.

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Y. Sugimoto, P. Pou, O. Custance, P. Jelinek, M. Abe, R. Prez, S. Morita, Complex patterning by vertical interchange atom manipulation using atomic force microscopy, Science 322, 413 (2008).

collaborative project that has an emphasis on SPM applications (Nanoobjetos). Within the European Union, the European Science Foundation sponsors or has sponsored several networks where the AFM has a key role such as Friction and Adhesion in Nanomechanical Systems (FANAS) or Nanotribology (Nanotribo).

> ADRIAN BACHTOLD Place and date of birth: London (UK), 1972 Education: University of Basel (Switzerland), Ph.D. Physics, 1999. Summa Cum Laude Experience Professor of ICN at the CIN2(ICN-CSIC) in Barcelona. Professor of CSIC at the CIN2(ICN-CSIC) in Barcelona. Principal investigator of the Quantum NanoElectronics group. Charg de recherche CNRS (permanent position) at the Ecole Normale. Suprieure in Paris Post doctoral Research, Delft university of technology. Post doctoral Research, University of California at Berkeley. PhD Research and Teaching Fellow, University of Basel. Research Field Nanophysics, quantum transport. Novel fabrication techniques at the nanometer scale. Carbon nanotubes, graphene. Electron transport at helium temperatures in nanostructures contacted by electrodes. Scanned probe microscopy of nanostructures. adrian.bachtold@cin2.es > FRANCISCO GUINEA Place and date of birth: Madrid (Spain), 1953 Experience Research scientist (permanent sta since 1987), Spanish National Research Council (CSIC) . Work in material models and nanoscopic devices, especially in graphene and related materials. About 300 scientic articles published. paco.guinea@icmm.csic.es > WOLFGANG MASER Place and date of birth: Koblenz (Germany), 1963 Education Diploma in Physics by University of Bonn (1990). PhD thesis performed at Max-Planck-Institute for Solid State Research (1990-1993). PhD in Natural Science of University of Tbingen (1993). Experience Postdoctoral stays at: Univ. of Sussex, 1993-1994), University of Montpellier (1994-1997) and the Instituto de Carboqumica (CSIC) (1997-2002). Research Scientist at Instituto de Carboqumica (CSIC) since 2002. Co-founder and scientic advisor of Nanozar S.L. (2005). Research topics cover low dimensional systems based on fullerenes, nanotubes, intrinsically conducting polymers and more recently graphene focussing on control of structure and property relationship. Current research relates to functional carbon nanotubes/graphene based composite materials. Author of more than 150 research articles. Conference chair of intern. ChemOnTubes 2008 conference. Board member of GDRI Graphene and Nanotubes. wmaser@icb.csic.es > STEPHAN ROCHE Place and date of birth: Grenoble (France), 1969 Education: Ph.D. in Physics Experience Centre de Investigaci en Nanocincia i Nanotecnologia Barcelona, Spain. Institute for Materials Science, TU-Dresden Dresden, Germany. Commissariat lEnergie Atomique Grenoble, France. Departamento de Fsica Terica, Universidad de Valladolid Valladolid, Spain. Department of Applied Physics, University of Tokyo Tokyo, Japan European Postdoc Fellow (EU-JSPS and EU-STF programmes). Centre National de Recherche Scientique, CNRS Grenoble, France. Ph.D. Candidate Sept. 1993 - Sept. 1996. sroche@cin2.es

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1. Introduction Carbon nanotubes and graphene are nanoscale objects of great scientic and technological interest due to a combination of extraordinary properties (metal or semiconductor for nanotubes, high mobility, good thermal conductor, sti, light, tough, high surface, etc.). It is a eld of research which has experienced an explosive growth since the discovery of nanotubes in 1991 and graphene in 2004. The Web of Science shows over 10771 scientic papers published in 2008, and at least 11178 in 2009, see Figure 1. The topics of research are very vast, including physics, chemistry, engineering, toxicology, and biomedicine.

below 50 /kg for multi-wall carbon nanotubes (MWNTs). Driving force is the demand for novel advanced composite materials with applications in automotive, aeronautics, sport goods, textiles and the eld of energy. Several companies have brought already advanced nanotube-composite materials on the market. While research on MWNTs more concentrates on dispersion and processing technologies towards advanced functional composites, there is an important research eort on single-wall carbon nanotubes towards improving growth, sorting (metal from semiconducting nanotubes) and assembling technologies. As for graphene, the rst fabricated layers were separated from graphite in a simple and inexpensive way using scotch tape. Other fabrication techniques were developed that are suitable for large-scale production, such as evaporation of SiC surfaces and chemical vapour deposition. Exfoliation methods leading to water soluble graphene oxide sheets which can be chemically reduced to graphene sheets open a broad ground for chemists and material scientists. Surprisingly, already there are several companies commercializing graphene based products such as Graphene Laboratories Inc. (USA), GrapheneEnergy (USA), Graphene Industries (UK) and Vorbeck Materials (DE). Products based on nanotube are already commercialized, such as batteries (longer life

Figure 1. Papers published worldwide since 2005 (date: 20 December 2009).

Today, various major international companies around the globe (European ones as major players) produce nanotubes on a several hundred tons/year scale and further up-scaling is still projected with a price expectation of

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time). Large electronic companies used nanotube eld-emitters to produce prototypes of at displays that can be rigid or exible. Composite materials made with graphene or nanotubes are promising for electric charge dissipation, electromagnetic shielding, reinforcement, thermal stability, high porosity. Scientic advances with potential applications include drug delivery, cell growth and repair, and transparent thin lm network transistors. There has been an intense activity in the last two years on the transport properties of graphene. The rst experiments on graphene showed that samples with dimensions of the order of 1-10 microns could be deposited on substrates above metallic gates. The carrier mobilities in the rst samples, =103 cm2 s-1 V -1, was about two orders of magnitude lower than those achieved in Si or GaAs devices. Nevertheless, the early samples showed the Integer Quantum Hall Eect, making them comparable in this respect to the best materials based on doped semiconductors. Large experimental eort ensued for improving the mobility (up to =2*105 cm2 s-1 V -1). Suspended graphene recently showed the Fractional Quantum Hall Eect. Finally, the combination of the electric and chemical properties of graphene allowed to use it as a detector of chemical species. Nanoelectromechancial systems (NEMS) with nanotubes and graphene have recently attracted a lot of interests. Mechanical resonators were fabricated that can be operated at ultra high frequencies and that can be used as ultrasensitive inertial mass sensors. The coupling of the mechanical and the charge degrees of freedom in nanotube resonators is strikingly strong as well as widely tuneable. Besides, it was shown that graphene can withstand up to 10% strain. Elastic strains change the dynamic of carriers in a similar way to a magnetic eld. It may lead to novel uses of graphene, not possible

with other materials, in topics such as mesoscopic magnetism, or strain engineering. Another important emerging direction of research concerns spin injection in graphene and nanotubes as well as spin manipulation possibilities. Although spin injection through ferromagnetic metal/semiconductor interfaces remains a great challenge, a spectacular advance made in 2007 demonstrated the strong capability of carbon nanotubes for converting the spin information into large electrical signals. The observation of relatively long spin relaxation times suggested that graphene could add some novelty to carbon-based spintronics. For instance, taking advantage of the long electronic mean free path and negligible spin-orbit coupling, the concept of a spin eld-eect transistor with a 2dimensional graphene channel has been proposed with an expectation of nearballistic spin transport operation. 2. Recent advances in Spain There are a number of very active research groups on graphene and nanotubes in Spain, with a signicant recognition in the eld. The Web of Science reports a substantial activity as shown in Figure 2. Interestingly, it can be seen that while on a worldwide level the publication activity in the last 4 years for nanotubes has less than doubled and almost reaches a saturation level, Spanish publication activity has more than tripled without reaching a saturation level. In the case of graphene, a rapidly increasing worldwide publication activity (ten-fold increase) can be noticed, while Spain merely doubled its publication activity in this eld in the same time frame. The situation is comparable to the beginning of nanotube research in Spain and underlines Spanish symptomatic weakness in rapidly conquering a new eld of research of great scientic and technological importance and marking the pace from the very beginning on.

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Figure 2. Papers from Spain published since 2005 (date: 20 December 2009).

2. Polymeric Modication of Graphene through Esterication of Graphite Oxide and Poly(vinyl alcohol). H.J. Salavagione, M.A. Gmez, G.Martnez. J. Materials Chemistry 19, 5027-5032 (2009). In this work novel poly(vinylalcohol)/reduced graphite oxide nanocomposites are presented. Synthesis is performed by reducing graphite oxide in the presence of the polymer matrix and coagulating the systems with 2-propanol. Interactions between polymer and reduced graphite oxide layers, mainly by hydrogen bonding, are observed. The interactions are responsible for remarkable changes in the thermal behaviour of the nanocomposites. In addition, high electrical conductivity has been achived at concentrations beyond 7.5 wt% of reduced graphite oxide (about 0.1 S/cm) with a percolation threshold between 0.5 and 1 wt%. 3. Ultralong natural graphene nanoribbons and their electrical conductivity. M. Moreno-Moreno, A. Castellanos-Gmez, G. Rubio-Bollinger, J. Gmez-Herrero, N. Agrat. Small 5(8):924-7 (2009). In this work reported by groups in UAM (Madrid), a new method for graphene ake deposition on surfaces based on silicone stamps is presented. Using high resolution optical and atomic force microscopy (AFM), the topography and electronic conductance of ultralong graphene nanoribbons with length greater than 30 m and minimum width below 20 nm are characterized. As the ribbons are consequence of the cleaving process (natural GNR) clean edges along the crystallographic graphene directions are expected, in contrast with those fabricated by lithography techniques.

It is a dicult exercise to summarise the activity on nanotube and graphene in Spain, especially since we (the authors of this report) are active players in the eld. We choose to select a set of published works that have in our opinion an important impact in the scientic community. Growth/synthesis 1. Nanobrillar polyaniline direct route to carbon nanotubes water dispersions in high concentrations P. Jimnez, W.K. Maser, P. Castell, M.T. Martnez, A.M. Benito Macromolecular Rapid Communications 30(6), 418 (2009) In this work the synthesis of a novel nanobrilar polyaniline/nanotube water dispersible nanocomposite is presented. The composite is easily dispersible in water at high concentrations up to 10 mg/ml even at highest nanotube loadings of 50 wt%. The in-situ polymerization has been carried out under nanobrilar conditions resulting in an intrinsically nanostructured composite materials responsible for the dispersibility in aquous dispersions. On the other hand, the synthesis represents a novel and direct route for obtaining nanotube dispersions at high concentrations without the use of any surfactant or stabilizers. The ndings are an important step towards an easy processing of nanotubes and composites

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from aquous dispersions into the forms of lms, bers and masterbatches.

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Applications 4. Subnanometer Motion of Cargoes Driven by Thermal Gradients along Carbon Nanotubes. A. Barreiro, R. Rurali, E.R. Hernndez, J. Moser, T. Pichler, L. Forr, A. Bachtold. Science 320, 775 (2008). An important issue in nanoelectromechanical systems is developing small electrically driven motors. The authors report on an articial nanofabricated motor in which one short carbon nanotube moves relative to another coaxial nanotube. A cargo is attached to an ablated outer wall of a multiwall carbon nanotube that can rotate and/or translate along the inner nanotube. The motion is actuated by imposing a thermal gradient along the nanotube, which allows for sub-nanometer displacements, as opposed to an electromigration or random walk eect. 5. Lable-Free DNA Biosensors Based on Functionalized Carbon Nanotube Field Eect Transistors. M.T. Martnez, Y-Chih Tseng, Nerea Ormategui, Iraida Loinaz, Ramn Eritja, Jerey Bokor. Nano Letters 9(2), 530 (2009). In this work a new approach to ensure the specic adsorption of DNA to nanotubes is presented. A carbon nanotube transistor array was used to detect DNA hybridization. A polymer poly(methylmethacrylate-co-poly (ethyleneglycol)methacrylate-co-N-succinimidyl methacrylate) was synthesized and bonded noncovalently to the nanotube. Aminated singlestrand DNA was then attached covalently to the polymer. After hybridization statistically signicant changes were observed in key transistor parameters. Hybridized DNA traps both electrons and holes, possibly caused by the charge-trapping nature of the base pairs. 6. Immediate detection of Living Bacteria at Ultralow Concentrations Using a Carbon
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Nanoube Based Potentiometric Aptasensor. G.A. Zelada-Guilln, Jordi Riu, Ali Dzgn, F. Xavier Rius. Angewandte Chemie, 48, 7334 (2009). In this work, it is demonstrated that easy-to-build aptamer-based SWCNT potentiometric sensors are highly selective and can be successfully used to detect living microorganisms in an assay in close to real time, thus making the detection of pathogens as easy as measuring the pH value. An aptamer attached to an electrode coated with single-walled carbon nanotubes interacts selectively with bacteria. The resulting electrochemical response is highly accurate and reproducible and starts at ultralow bacteria concentrations, thus providing a simple, selective method for pathogen detection. The most important strength of this biosensor is that simple positive/negative tests can be carried out in real zero-tolerance conditions and without cross reaction with other types of bacteria. The ease with which measurements are taken in potentiometric analysis opens the door to greater simplicity in microbiological analysis. 7. Impedimetric genosensors employing COOHmodied carbon nanotube screen-printed electrodes. A. Bonanni, M. J. Esplandiu, M. del Valle. Biosensors & Bioelectronics 24 (9), 2885-2891. In this work screen-printed electrodes modied with carboxyl functionalized multi-walled carbon nantoubes were used as platforms for impedimetric genosensing of oligonucleotide sequences specic for transgenic insect resistant Bt maize. After covalent immobilization of aminated DNA probe using carbodiimide chemistry, the impedance measurement was performed in a solution containing the redox marker. A complementary oligomer target was added, its hybridization promoted. Changes in charge transfer resistances between solution and electrode surface conrm the hybrid formation.

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8. Giant Magnetoresistance in Ultrasmall Graphene Based Devices. F. Muoz-Rojas, J. Fernndez-Rossier, and J. J. Palacios. Phys. Rev. Lett. 102, 136810 (2009). By computing spin-polarized electronic transport across a nite zigzag graphene ribbon bridging two metallic graphene electrodes, devices featuring 100% magnetoresistance are demonstrated to be achievable built entirely out of carbon. In the ground state a short zigzag ribbon is an antiferromagnetic insulator which, when connecting two metallic electrodes, acts as a tunnel barrier that suppresses the conductance. The application of a magnetic eld makes the ribbon ferromagnetic and conductive, increasing dramatically the current between electrodes. Large magnetoresistance is found in this system at liquid nitrogen temperature and 10 T or at liquid helium temperature and 300 G. 9. Carbon Nanoelectronics: Unzipping Tubes into Graphene Ribbons. H. Santos, L. Chico, and L. Brey. Phys. Rev. Lett. 103, 086801 (2009). This paper reports on a theoretical study of transport properties of novel carbon nanostructures made of partially unzipped carbon nanotubes, which can be regarded as a seamless junction of a tube and a nanoribbon. Graphene nanoribbons are found to act at certain energy ranges as perfect valley lters for carbon nanotubes, with the maximum possible conductance. These results show that a partially unzipped carbon nanotube is a magnetoresistive device, with a very large value of magnetoresistance. The properties of several structures combining nanotubes and graphene nanoribbons are explored, demonstrating that they behave as optimal contacts for each other, and opening a new route for the design of mixed graphene-nanotube devices.

The authors study the changes induced by the eective gauge eld due to ripples on the low energy electronic structure of graphene. They show that zero-energy Landau levels can form due to the smooth deformation of the graphene layer. The existence of localized levels gives rise to a large compressibility at zero energy and to the enhancement of instabilities arising from electron-electron interactions including electronic phase separation. The combined eect of the ripples and an external magnetic eld breaks the valley symmetry of graphene, leading to the possibility of valley selection. 11. Ab initio study of transport properties in defected carbon nanotubes: an O(N) approach. B. Biel, F. J. Garca-Vidal, A. Rubio, F. Flores. Journal Of Physics Condensed Matter 20, 294214 - 8 (2008). This work by B. Biel (currently at the University of Granada) and coworkers reports on a combination of ab initio simulations and linearscaling Green's functions techniques to analyze the transport properties of long (up to one micron) carbon nanotubes with realistic disorder. The energetics and the inuence of single defects (mono- and di-vacancies) on the electronic and transport properties of single-walled armchair carbon nanotubes are analyzed as a function of the tube diameter by means of the local orbital rst-principles Fireball code. Ecient O(N) Green's functions techniques framed within the Landauer-Buttiker formalism allow a statistical study of the nanotube conductance averaged over a large sample of defected tubes and thus extraction of the nanotubes localization length. Both the cases of zero and room temperature have been addressed.

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Electron transport

10. Midgap states and charge inhomogeneities in corrugated graphene. F. Guinea, M. I. Katsnelson, M. A. H. Vozmediano. Phys. Rev. B 77, 075402 (2008).

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Nanoelectromechanical systems 12. Ultra Sensitive Mass Sensing with a Nanotube Electromechanical Resonator. B. Lassagne, D. Garca-Snchez, A. Aguasca, and A. Bachtold. Nano Letters 8, 3735 (2008). Shrinking mechanical resonators to submicrometer dimensions has tremendously improved capabilities in sensing applications. In this letter, the authors go further in size reduction using a 1 nm diameter carbon nanotube as a mechanical resonator for mass sensing. The performances, which are tested by measuring the mass of evaporated chromium atoms, are exceptional. The measured mass responsivity and mass resolution are excellent; they surpass the values reported previously for resonators made of nanotube and of any other material. 13. Coupling Mechanics to Charge Transport in Carbon Nanotube Mechanical Resonators. B. Lassagne, Y. Tarakanov, J. Kinaret, D. GarcaSnchez, A. Bachtold. Science 325, 1107 (2009). Nanoelectromechanical resonators have potential applications in sensing, cooling, and mechanical signal processing. An important parameter in these systems is the strength of coupling the resonator motion to charge transport through the device. Authors investigate the mechanical oscillations of a suspended single-walled carbon nanotube that also acts as a single-electron transistor. The coupling of the mechanical and the charge degrees of freedom is strikingly strong as well as widely tuneable. 14. Energy gaps, topological insulator state and zero-eld quantum Hall eect in graphene by strain engineering. F. Guinea, M. I. Katsnelson, A. K. Geim. Nature phys. 6, 30 (2009). Owing to the fact that graphene is just one atom thick, it has been suggested that it might be

possible to control its properties by subjecting it to mechanical strain. New analysis indicates not only this, but that pseudomagnetic behaviour and even zero-eld quantum Hall eects could be induced in graphene under realistic amounts of strain. Spintronics 15. Transformation of spin information into large electrical signals using carbon nanotubes L. E. Hueso, J. M. Pruneda, V. Ferrari, G. Burnell, J. P. Valds-Herrera, B. D. Simons, P. B. Littlewood, E. Artacho, Albert Fert & Neil D. Mathur, Nature 445, 410 (2007). In this paper, L. Hueso (currently head of the nanodevice groups at CIC-NANOGUNE in San Sebastian) and coworkers have demonstrated the strong potential of carbon based materials for the development of coherent spintronics. Indeed, due to the intrinsically spin orbit coupling, very long spin diusion lengths were obtained, allowing for giant magnetoresistance signals to be measured. Simulations performed by Miguel Pruneda (now permanent research at CIN2-Barcelona) have conrmed the good interface matching between metals and nanotubes. 3. Selection of International Publications (2007-2009) Growth/chemistry A Chemical Route to Graphene for Device Applications. S. Glje, S. Han, M. Wang, K. L. Wang, R.B. Kaner Nano Letters, 7(11), 3394 (2007). Charting Large-Area Synthesis of High-Quality and Uniform Graphene Films on Copper Foils. X. Li, Weiwei Cai, Jinho An, S. Kim, J. Nah, D. Yang, R. Piner, A. Velamakanni, I. Jung, E. Tutuc, S. K. Banerjee, L. Colombo, and R. S. Ruoff Science 324, 1312 (2009). Preferential Growth of Single-Walled Carbon Nanotubes with Metallic Conductivity.
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An atomic-resolution nanomechanical mass sensor. K. Jensen, K. Kim, and A. Zettl. Nature Nanotech. 3 (9), 533-537 (2008). Measurement of the elastic properties and intrinsic strength of monolayer graphene. Lee, C., Wei, X., Kysar, J., Hone J. Science 321, 385-388 (2008). Coupling Mechanics to Charge Transport in Carbon Nanotube Mechanical Resonators. B. Lassagne, Y. Tarakanov, J. Kinaret, D. GarcaSanchez, A. Bachtold. Science 325, 1107 (2009). Energy gaps and a zero-eld quantum Hall eect in graphene by strain engineering. Guinea F., Katsnelson, M. I., Geim, A. K., Nature Phys. 6, 30 (2009). Spintronics

Applications Transparent, Conductive Graphene Electrodes for Dye-sensitized Solar Cells. X. Wang, L. Zhi, K. Mllen. Nano Letters 8(1), 323 (2008). Lable-Free DNA Biosensors Based on Functionalized Carbon Nanotube Field Eect Transistors M.T. Martnez, Y-Chih Tseng, Nerea Ormategui, Iraida Loinaz, Ramn Eritja, Jeffrey Bokor. Nano Letters 9(2), 530 (2009). Electron transport Approaching ballistic transport in suspended graphene. Xu, D., Skachko, I., Barker, A., Andrei, E. Y. Nature Nano 3, 491-495 (2008). Observation of a Mott Insulating State in Ultra-Clean Carbon Nanotubes. V. V. Deshpande, B. Chandra, R. Caldwell, D. Novikov, J. Hone, M. Bockrath. Science 323, 106 (2009). Fractional quantum Hall eect and insulating phase of Dirac electrons in graphene. X. Du, I. Skachko, F. Duerr, A. Luican, E. Y. Andrei Nature 462, 192 (2009). Observation of the fractional quantum Hall eect in graphene. K.I. Bolotin, F. Ghahari, M. D. Shulman, H.L. Stormer, P. Kim. Nature 462, 196 (2009).

Transformation of spin information into large electrical signals using carbon nanotubes. L. E. Hueso, J. M. Pruneda, V. Ferrari, G. Burnell, J.P. Valdes-Herrera, B. D. Simons, P.B. Littlewood, E. Artacho, Albert Fert & Neil D. Mathur. Nature 445, 410 (2007). Electronic spin transport and spin precession in single graphene layers at room temperature. N. Tombros, C. Jozsa, M. Popinciuc, H.T. Jonkman, B.J.V Wees. Nature 448, 571 (2007). 4. Proposed actions to initiate in Spain Actions proposed are related to the following problems encountered in the eld of graphene and nanotube research.

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A.R. Harutyunyan, G. Chen, T.M. Paronyan, E.M. Pigos, O.A. Kuznetsov, K. Hewaparakrama, S.M. Kim, D.Zakharov, E.A. Stach, G.U. Suanasekera. Science, 326, 116 (2009).

Nanoelectromechanical systems

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Lack of critical mass carrying out high gain/high risk research in a topic of importance at the forefront of science, sufficient funding for research projects in a topic at the forefront of science, especially with respect to contracting qualified personal (PhD and postdocs), international initiatives and visibility, private R&D support, efficient (rapid and flexible) instruments to support new research developments. To overcome these problems, the following actions are proposed: More generous funding of strategic research projects (graphene, nanotubes), especially with respect to have available funds for contracting PhD students or postdocs as well as leading senior scientist to gain the necessary critical mass for carrying out research at the forefront of science. ERC-type grants at the national level should be launched (well funded grants for single groups). Active participation and funding of international research initiatives (related to graphene and carbon nanotubes) such as ESF programmes. Promote formation of young researchers in field of nanotubes and graphene by corresponding PhD scholarships, introducing the topic in Master Courses in Nanotechnology. Enhance visibility of Spanish research in field of graphene and nanotubes by promoting and generously supporting international events on these. Promote private R&D effort in fields related to graphene and nanotube related research.

Support the creation of spin-off companies as important technology platform which provides new impulses to industry in different sectors. 5. Future infrastructures (2010-2013) Creation of multiple medium-size clean rooms through the country within existing research centres. This will allow for increased flexibility of operation as well as better access. Typical budgets could range between 1 and 3 M. One or two technicians can be enough. Increase of the number of highly qualified technical personnel. Improvement of institutional links between educational programs and research centers. There are several emerging research centers in Spain that are attracting excellence and develop new initiatives to foster the development of nanoscience and nanotechnology. However, there is a clear problem to attract Spanish citizens to do a PHD or a post doc. One solution is to foster (or create) masters in nanoscience by suited reinforcement of technical and administrative personal, as well as teaching assistants and research sta. A coordination, or even networking, of Nanoscience educational programs at the national level would be desirable. 6. Relevant Initiatives 6.1 Spain NANOSPAIN Network. TNT conference. Sociedad de Materiales Espaola. Red Espaola de Micro y Nanosistemas IBERNAM. ChemOnTubes Conference.

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CSIC Research centres (CIN2, CNM, ICB, ICMM, ICTP, IFM-UPV). Regional Research centres (CIC-Nanogune, ICN, Imdea). Universities (Alicante, Barcelona, Madrid, Salamanca, Zaragoza). Private research centres (AlphaSip S.L. in Madrid, DropSens S.L. in Oviedo, Nanoinnova SL in Madrid, Nanozar S.L. in Zaragoza). 6.2 Europe
Figure 3. Suspended graphene structured in a Hall bar (J. Moser and A. Bachtold, CIN2-Barcelona)

GDR Network. This is an international research network supported by CSIC and other institutions in the world, such as the CNRS in France and Cambridge in the UK. TNT conference. 7. Conclusions Spanish research contributes with important results to the eld of carbon nanotubes and graphene. The number of publications in international journals has increased over the last years. Here, the activity on theory produces highest impact publications. On the experimental side high impact research is carried out by few groups but lack of critical mass, funding and proper early initiatives are serious and continuous danger for being competitive with large international research teams. Visibiltiy of Spanish research has increased (also by international networking), but a satisfactory level of international recognition is not reached yet. On the other hand, solid results of nanotube and graphene research produced in eld of materials science, chemistry and energy bear a high potential for direct technology transfer towards

various industrial sectors as shown by the creation of several Spanish spin-o companies. The golden opportunities nanotube and graphene research oer should not be missed and thus more generous funding for corresponding research projects is required as well as the promotion of private R&D initiatives and fostering the link between academics and industry.

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Plataforma Tecnolgica Espaola de Materiales Avanzados y Nanomateriales.

> JUAN JOS SENZ Place and date of birth Madrid (Spain), 1960 Education Professor at the Condensed Matter Physics Department of the Universidad Autnoma de Madrid (UAM). Since 1993 he runs the Moving Light and Electrons (MoLE) group at UAM. Experience He joined the UAM as Assistant Professor in 1982 where he worked on the stability and equilibrium properties of small clusters and crystals in Prof. N. Garcas group. He was also involved in the rst works on magnetic force microscopy (MFM) in collaboration with Prof. Gntherodts group in Basel. In 1987 he obtained his PhD from UAM. During his post-doc, he worked on electron eld emission from nanotips in Dr. H. Rohrers group at IBM-Zrich. From 1989 to 2006 he was Associate Professor at UAM. Since 2007 he is Full Professor at UAM. At present his research interests include theoretical modelling of scanning probe microscopies (SPM), quantum electron transport through nanocontacts and wave transport and molecular imaging through complex media. In 2003 he was Invited Professor in the EM2C-(CNRS) Lab. at cole Centrale Paris working on nanoscale thermal transport and nano-optics. He has published over 120 papers (among them 26 in Physical Review Letters) with more than 2300 citations and presented more than 150 communications in international conferences. He is co-organizer of the Trends in Nanotechnology (TNT) conference series. He is involved in the European FP7 NANOMAGMA (NANOstructured active MAGnetoplasmonic Materials) project and coordinates the Comunidad de Madrid Program MICROSERES. juanjo.saenz@uam.es

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1. Introduction During the past 20 years, the fundamental techniques of theory, modelling, and simulation have undergone a revolution that parallels the extraordinary experimental advances on which the new eld of nanoscience is based. This period has seen the development of density functional algorithms, quantum Monte Carlo techniques, ab initio molecular dynamics, advances in classical Monte Carlo methods and mesoscale methods for soft matter, and fastmultipole and multigrid algorithms. Dramatic new insights have come from the application of these and other new theoretical capabilities. Simultaneously, advances in hardware increased power by more than four orders of magnitude. The combination of new theoretical methods together with increased computing power has made it possible to simulate systems with millions of degrees of freedom. Although theory and modelling has played a key role in the development and improvement of industrial applications, so far modelling at the nanoscale has been mainly aimed at support research and at explaining the origin of observed phenomena. This is certainly the most important role in fundamental science. However, in order to meet the needs of the industry and to make practical exploitation of new device and solidstate or molecular material concepts possible, a

new integrated approach to modelling at the nanoscale is needed. A hierarchy of multi-scale tools must be set up, in analogy with what already exists for microelectronics, although with a more complex structure resulting from the more intricate physical nature of the devices. 2. State of the art1 Although the required integrated platforms need to be developed, the eorts made in the last few years by the modelling community have yielded signicant advances in terms of quantitatively reliable simulation and of ab-initio capability, which represent a solid basis on which a true multi-scale, multi-physics hierarchy can be built. 2.1 Electronic transport simulations and industrial needs The most widely used codes for ab-initio simulations of solids and extended systems rely on the use of the Density Functional Theory (DFT), rather than on Quantum Chemistry methods. Many of them have been developed in Europe, and some of them are commercial, although their use is mostly limited to the academic community. Among the most popular DFT codes using local atomic orbitals as a basis set we can mention the order-N code SIESTA2 which uses a basis set of numerical atomic orbitals.

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In response to the industrial need of new simulation tools, a class of quantum and transport solvers is emerging. However, they do not include any inelastic scattering mechanism, and thus are not suitable for the calculation of transport properties in near-future devices. On the other hand, high-level device simulation tools are at an early stage of development in universities and research institutions. However, such simulation tools are in general dicult to use in an industrial environment, in particular because of a lack of documentation, support and graphical user interface. 2.2 Material Science and devices For most emerging devices, the distinction between material and device simulation is getting increasingly blurred, because at low dimensional scales the properties of the material sharply diverge from those of the bulk or of a thin lm and become strongly dependent on the detailed device geometry. Computational physics and quantum chemistry researchers have been developing sophisticated programs to explicitly calculate the quantum mechanics of solids and molecules from rst principles. Since quantum mechanics determines the charge distributions within materials, all electrical, optical, thermal and mechanical properties, in fact any physical or chemical property can in principle be deduced from these calculations. However, even at the DFT level, ab initio calculations are computationally too demanding to perform realistic simulations of devices. Therefore, it is necessary to develop more approximate methods and, nally, to combine them in the so-called multi-scale approaches, in which dierent length scales are described with dierent degrees of accuracy and detail. This convergence between material and device

studies also implies that a much more interdisciplinary approach than in the past is needed, with close integration between chemistry, physics, engineering, and, in a growing number of cases, biology. 2.3 Carbon-based electronics and spintronics Amongst the most promising materials for the development of beyond CMOS nanoelectronics, Carbon Nanotubes & Graphene-based materials and devices deserve some particular consideration. Indeed, their unusual electronic and structural physical properties promote carbon nanomaterials as promising candidates for a wide range of nanoscience and nanotechnology applications. To date, the development of nanotubes and graphene science have been strongly driven by theory and quantum simulation. The great advantage of carbon-based materials and devices is that, in contrast to their siliconbased counterparts, their quantum simulation can be handled up to a very high level of accuracy for realistic device structures. The complete understanding and further versatile monitoring of novel forms of chemicallymodied nanotubes and graphene will however lead to an increasing demand for more sophisticated computational approaches, combining rst principles results with advanced order N schemes to tackle material complexity and device features, as developed in some recent literature (see below). 2.4 Nano-Bio modelling The theoretical understanding of the bio/inorganic interface is in its infancy, due to the large complexity of the systems and the variety of dierent physical interactions playing a dominant role. Further, state of the art simulation techniques for large biomolecular

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Moreover, due to the highly dynamical character of biomolecular systems -seen e.g. in the presence of multiple time scales in the atomic dynamics- the electronic structure is strongly entangled with structural uctuations. We are thus confronting the problem of dealing with the interaction of strongly uctuating complex molecules with inorganic systems (substrates, etc). 2.5 Thermoelectric energy conversion The importance of research on thermoelectric energy conversion is growing in parallel with the need for alternative sources of energy. With the recent developments in the eld, thermoelectric energy generators have become a commercial product in the market and their eciencies are improving constantly, but the commercially available products did not take the advantage of nano-technology yet. In fact, thermoelectricity is one of the areas in which nano-scale fabrication techniques oer a breakthrough in device performances. 2.6 Multifunctional oxides Multifunctional oxides, ranging from piezoelectrics to magnetoelectric multiferroics, oer a wide range of physical eects that can be used to our advantage in the design of novel nanodevices. For example, these materials make

These are just two examples of many novel applications that add up to the more traditional ones -as sensors, actuators, memories, highlytunable dielectrics, etc.- that can now be scaled down to nanometric sizes by means of modern deposition techniques. The contribution from simulations to resolve more applied problems (e.g, that of the integration with silicon) is just starting, and it is a major challenge that will certainly generate a lot of activity in the coming years. 2.7 Nanophotonics Another example where multi-scale and multiphysics simulations become essential is represented by the eort to merge electronics with nanophotonics. The integration of CMOS circuits and nanophotonic devices on the same chip opens new perspectives for optical interconnections as well as in the data processing. These involve the modelling of standard passive components, such as waveguides, turning mirrors, splitters and input and output couplers, as well as active elements, such as modulators and optical switches. This requires the development of new numerical tools able to describe electromagnetic interactions and light propagation at dierent length scales. They should be able to describe the electromagnetic eld from the scale of a few light wavelengths (already of the order of the whole micro-device) down to the nanometer scale elements.

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systems are to a large degree still based on classical physics approaches (classical molecular dynamics, classical statistical physics); while this can still provide valuable insight into many thermodynamical and dynamical properties, a crucial point is nevertheless missing: the possibility to obtain information about the electronic structure of the biomolecules, an issue which is essential in order to explore the eciency of such systems to provide charge migration pathways.

it possible to implement a variety of tunable and/or switchable eld eects at the nanoscale. Thus, a magnetoelectric multiferroic can be used to control the spin polarization of the current through a magnetic tunnel junction by merely applying a voltage; or a piezoelectric layer can be used to exert very well controlled epitaxiallike pressures on the adjacent layers of a multilayered heterostructure.

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These new tools should include a realistic description of the optical properties including electroand magneto-optical active nanostructures and plasmonic elements which are expected to be key ingredients of a new generation of active optoelectronic components. 2.8 NEMO devices A mayor challenge of the multi-physical modelling will be to simulate a full nano-device where electronics, mechanics and photonics meet at the nanoscale. The interaction of an optical eld with a device takes place not only through the electromagnetic properties, but also through the mechanical response (radiation pressure forces). The physical mechanisms and possible applications of optical cooling of mechanical resonators are being explored. Modelling NanoElectro-Mechano-Optical (NEMO) devices is going to play a key (and fascinating) role in the development and optimization of new transducers and devices. Thus, one of the main challenges for modelling in the next few years is the creation of well organized collaborations with a critical mass sucient for the development of integrated simulation platforms and with direct contacts with the industrial world. 3. Some relevant publications (2007-2009) We have selected 10 publications related with theory and modelling relevant in Nanoscience and Nanotechnology in the period 2007-2009 based on data from ISI Web of Knowledge3: The publications cover most of the hot topics in Nanoscience from the electronic properties of graphene, thermal transport and energy harvesting with nanowires, new nanostructured multiferroic composites and metallic alloys,

quantum dots and spintronic and light interaction with nanostructures to mention a few. A.H. Castro Neto, F. Guinea, N. M. R. Peres, et al. The electronic properties of graphene. Reviews of Modern Physics, 81 (1), 109-162 (Jan 2009). J. C. Meyer, A. K. Geim, M. I. Katsnelson, et al. The structure of suspended graphene sheets, Nature, 446 (7131), 60-63 (Mar 2007). A. I. Hochbaum, R. K. Chen, R. D. Delgado, et al Enhanced thermoelectric performance of rough silicon nanowires. Nature, 451 (7175), 163-U5 (Jan 2008). B. Z. Tian, X. L. Zheng, T. J. Kempa, et al. Coaxial silicon nanowires as solar cells and nanoelectronic power sources. Nature, 449 (7164 ), 885-U8 (Oct 2007). A. I. Boukai, Y. Bunimovich, J. Tahir-Kheli, et al. Silicon nanowires as efficient thermoelectric materials. Nature, 451 (7175), 168-171 (Jan 2008). C. W. Nan, M. I. Bichurin, S. X. Dong, et al. Multiferroic magnetoelectric composites: Historical perspective status and future directions. Nature Nanotechnology, 3 (1), 31-35 (Jan 2008). C. A. Schuh, T. C. Hufnagel, U. Ramamurty. Overview No.144 - Mechanical behavior of amorphous alloys. Acta Materialia, 55 (12) 4067-4109 (Jul 2007). R. Hanson, L. P. Kouwenhoven, J. R. Petta, et al. Spins in few-electron quantum dots. Reviews of moderm Physics, 79 (4), 1217-1265 (Oct 2007). J. C. Charlier, X. Blase, S.Roche. Electronic and transport properties of nanotubes. Reviews of moderm Physics, 79 (2), 677-732 (Apr 2007).

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4. Networking for modelling in Spain, Europe and the United States In the United States, the network for computational nanotechnology (NCN) is a sixuniversity initiative established in 2002 to connect those who develop simulation tools with the potential users, including those in academia, and in industries. The NCN has received a funding of several million dollars for 5 years of activity. One of the main tasks of NCN is the consolidation of the nanoHUB.org simulation gateway (http://nanohub.org/home), which is currently providing access to computational codes and resources to the academic community. The growth of the NCN is likely to attract increasing attention to the US computational nanotechnology platform from all over the world, from students, as well as from academic and, more recently, industrials researchers. In Europe an initiative similar to the nanoHUB, but on a much smaller scale, was started within the Phantoms network of excellence (http://vonbiber.iet. unipi.it) and has been active for several years; it is currently being revived with some funding within the EUNanoICT coordinated action. In a context in which the role of simulation might become strategically relevant for the development of nanotechnologies, molecular nanosciences, nanoelectronics, nanomaterial science nanophotonics and nanobiotechnologies, it seems urgent for Europe to set up a computational platform infrastructure similar to NCN, in order to ensure its positioning within the international competition. The needs are manifold. First, a detailed identication of

5. Specic actions to be undertaken (2010-2013) An extension of the M4NANO initiative could pave the way towards the development of a European Modelling Database. An initiative similar to the American NCN would also be needed in Europe in conjunction between the EUs ICT and NMP programs, since the full scope from materials to devices and circuits should be addressed. These novel initiatives should be able to bridge advanced ab-initio/atomistic computational

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F. Krausz, M. Ivanov. Attosecond physics. Reviews of moderm Physics, 81 (1), 163-234 (Jan 2009).

European initiatives and networks must be performed, and de-fragmentation of such activities undertaken. A pioneer initiative has been developed in Spain through the M4NANO database (www.m4nano.com) gathering all nanotechnology-related research activities in modelling at the national level. This Spanish initiative could serve as a starting point to extend the database to the European level. Second, clear incentives need to be launched within the European Framework programmes to encourage and sustain networking and excellence in the eld of computational nanotechnology and nanosciences. To date, no structure such as a Network of Excellence exists within the ICT programme, although the programme NMP supported a NANOQUANTA NoE in FP6, and infrastructural funding has been provided to the newly established ETSF (European Theoretical Spectroscopy Facility, www.etsf.eu). This network mainly addresses optical characterization of nanomaterials, and provides an open platform for European users, that can benet from the gathered excellence and expertise, as well as standardized computational tools. There is also a coordinated initiative focused on the specic topic of electronic structure calculations, the Psi-k network (www.psi-k.org).

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approaches to ultimate high-level simulation tools such as Technology Computer-Aided Design (TCAD) models that are of crucial importance in software companies. Many elds such as organic electronics, spintronics, beyond CMOS nanoelectronics, nanoelectromechanical devices, nanosensor or nanophotonics devices denitely lack standardized and enabling tools that are however mandatory to assess the potential of new concepts, or to adapt processes and architectures to achieve the desired functionalities. The European excellence in these elds is well known and in many aspects overcomes that of the US or of Asian countries.

interface that is not suitable for usage in an industrial environment. There is therefore a need for integration of advanced modelling tools into simulators that can be prociently used by device and circuit engineers: they will need to include advanced physical models and at the same time be able to cope with variability and uctuations, which are expected to be among the greatest challenges to further device downscaling. It is clear that the time is ripe for a new generation of software tools, whose development is of essential importance for the competitiveness and sustainability of European industry, and which requires a coordinated eort of all the main players.

Figure 1. Functionalized graphene nanoribbons can be used to detect organic molecules.

6. Conclusions Recent advances in nanoscale device technology have made traditional simulation approaches obsolete from several points of view, requiring the urgent development of a new multiscale modelling hierarchy, to support the design of nanodevices and nanocircuits. This lack of adequate modeling tools is apparent not only for emerging devices, but also for aggressively scaled traditional CMOS technology, in which novel geometries and novel materials are being introduced. New approaches to simulation have been developed at the academic level, but they are usually focused on specic aspects and have a user
Figure 2. The classical diusion of a small particle in a uid can be greatly enhanced by the light eld of two interfering laser beams. Langevin Molecular Dynamics simulations show that radiation pressure leads to a giant acceleration of free diusion. [Albaladejo et al., Nano Letters 9, 3527 (2009)] (Courtesy of Silvia Albaladejo).

References Based on M. Macucci et al, Status of modelling for nanoscale and information processing and storage devices, E-Nano Newsletter 16, 5 (2009). (www.phantomsnet.net/les/E_NANO_NEWS/ E_NANO_Newsletter_Issue16.pdf).
1

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Data obtained by on-line search in the ISI Web of Knowledge among the most cited papers published in the period 2007-2009 (Publication year) having more than 48 citations per year. The list was completed by searching (in topic) for nano* and simul*, nano* and theor* and nano* and model*.

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J. M. Soler, E. Artacho, J. D. Gale, A. Garca, J. Junquera, P. Ordejn, D. Snchez-Portal, The SIESTA method for ab initio order-N materials simulations, Journal of Physics: Condensed Matter 14, 2745(2002). (www.icmab.es/siesta).

Emerging N&N Centers in Spain

IMDEA Nanociencia CIC nanoGUNE Consolider Instituto Catal de Nanotecnologia (ICN) Instituto de Nanocincia i Nanotecnologia (CIN2UB) The Institute of Photonic Sciences (ICFO) Institute of Nanoscience of Aragon (INA) Andalusian Centre for Nanomedicine and Biotechnology (BIONAND) International Iberian Nanotechnology Laboratory (INL) Valencia Nanophotonics Technology Center (NTC) Nanomaterials and Nanotechnology Research Center (CINN)

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NANOSCIENCE & NANOTECNOLOGY IN SPAIN: CENTERS

IMDEA Nanociencia (Madrid Institute for Advanced Studies in Nanosciences)

Opening: The building of IMDEA Nanocience Institute, located in the UAM Cantoblanco campus, will be operative in October 2011. Provisional headquarter: UAM. Facultad de Ciencias; Mdulo C-IX. 3rd oor. Activity Areas

Facultad de Ciencias; Mdulo C-IX, 3 planta Avda. Fco. Toms y Valiente, 7 Ciudad Universitaria de Cantoblanco 28049 Madrid Tel +34 91 497 6849 / 51 e-mail: contacto.nanociencia@imdea.org web: www.nanociencia.imdea.org

Program 1. Molecular nanoscience Design and Synthesis of Molecular Nanostructures and Nanomaterials. Atomic and Molecular Self-assembly at Surfaces and Spectroscopy on Molecular Systems. Program 2. Scanning Probe Microscopies and Surfaces Advanced Microscopies and Local Spectroscopies. Inelastic Spectroscopy at Surfaces. Program 3. Nanomagnetism Magnetic Nanomaterials. Biomedical Applications. Program 4. Nanobiosystems: Biomachines and Manipulation of Macromolecules Single-molecule Analysis of Macromolecular Aggregates. Organization of Macromolecular Aggregates on Defined Substrates. Program 5. Nanoelectronic and superconductivity Electric Transport in Nanosystems. Superconducting Nanostructures. Program 6. Semiconducting Nanostructures and Nanophotonics Semiconducting Nanostructures for Quantum Information. Nanophotonics.

Summary: The IMDEA Nanociencia Foundation, created by a joint initiative of the regional Government of Madrid and the Ministry of Science and Education of the Government of Spain, manages the IMDEA Nanociencia Institute. This new interdisciplinary research centre aims at becoming a exible framework to create new internationally competitive research groups by hybridizing some of the best scientists in Madrid dedicated to the exploration of basic nanoscience with recognized researches recognized elsewhere recruited on an internationally competitive basis.

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Horizontal Program on Nanofabrication and Advanced Instrumentation Employees Researchers (including associated) 19 / PostDoctoral Researches 6 / PhD students 6 / Management Sta 3. For more information see web www.nanociencia.imdea.org Infrastructure (from 100.000) Low-Temperature Scanning Tunnelling Eect Microscope (STM); Femtosecond spectroscopic instrumentation; Atomic Force and Fluorescence Microscope. Projects / Funding DOTUBE (FP7- Marie Curie Actions-PEOPLEERG-2008). BIONANOTOOLS (FP7- Marie Curie ActionsPEOPLE-IRG-2008). Crecimiento y caracterizacin de nuevos nanomateriales basados en el autoensamblado de puntos cuanticos y nanotubos de carbono sobre superficies slidas (MAT2009-MICINN). AMAROUT (FP7-Marie Curie Actions-PEOPLECOFUND-2008) (IMDEA Nanociencia as a part). 2008 annual budget in M (including salaries) and an estimation when fully operating. This information is subject to the Spanish Legislation on Privacy (Ley Orgnica 15/99 LOPD) and could not be provided.

CIC nanoGUNE Consolider

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Tolosa Hiribidea, 76 E-20018 Donostia - San Sebastin Tel. 943 574 000 Contact person / e-mail Jos Mara Pitarke de la Torre/ jm.pitarke@nanogune.eu web: www.nanogune.eu

Summary: The CIC nanoGUNE Consolider is a newly established Center created with the mission of addressing basic and applied world-class research in nanoscience and nanotechnology, fostering highstandard training and education of researchers in this eld, and promoting the cooperation among the dierent agents in the Basque Science, Technology, and Innovation Network (Universities and Technological Centers) and between these agents and the industrial sector. Opening date: 30th January 2009 Activity Areas NANOMAGNETISM GROUP CIC1 Magnetization reversal, dynamics, and related characterization methods.

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Fabrication and magnetic properties of multilayered magnetic materials. Fabrication and characterization of magnetic nano-structures. NANOOPTICS GROUP CIC2 Ultra-broadband near-field optical microscopy. Near-field optical characterization of nanoscale materials and semiconductor devices. Near-field characterization of photonic structures. SELF-ASSEMBLY GROUP CIC3 Plant viruses as scaffolds for nanoscale structures. Electrospinning of self-assembling material to wires . NANOBIOTHECNOLOGY GROUP CIC4 Energy transfer processes in hybrid materials for chemical and biological fuel production, biophotonic and photovoltaic applications. Biomedical diagnostics using the energy transfer processes. Ultrasensitive nanocrystal-based pathogen detection employing the energy transfer processes. NANODEVICES GROUP CIC5 Carbon-based spintronics Multifunctional devices Nanofabrication Employees 2009 Sta: 22 Others: 18 2010 Sta: 23 Others: 30

Forecast 2015 Sta: 35 Others: 65 Infrastructure (from 100.000) 150TWO Ultra High Resolution E-Beam Tool Deposition System Vibrating Sample Magnetometer QD-SQUID VSM QD-PPMS (Phiysical Property Measurement System) Laser Confocal Microscope WITec Confocal Raman Microscope System Alpha300 R Em-CCD ATC 2200 UHV Sputtering System Scanning Near-eld Optical Microscope System EVG620 Double Side Mask AFM/STM Microscope Agilent 5500 Univex 350 for Thermal and E-Beam Evaporation Base, Acid and Solvent Wetbench HF Probe Station from Lake Shore 4ALD system Savannah 100 Fisher equipment Flux Cytometer CyAn-ADP from Beckman coulter Nanofabrication tools Ion Beam Etching System UHV Ebeam Thermal Deposition System Reactive Ion Etcher Ultra High Resolution E-Beam Lithography Tool UHV Sputtering System Mask Aligner Atomic Layer Deposition System Characterization tools High Resolution (Scanning) Transmission Electron Microscope Environmental Scanning Electron Microscope (SEM/ESEM) Dual-Beam Focused Ion Beam X-Ray Diffractometer FTIR Spectrometer

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Confocal Raman Microscope Laser Confocal Microscope Physical Properties Measurement System (PPMS/QD-SQUID) Scanning Near-field Optical Microscope AFM/STM Microscopes Cytometer

Institut Catal de Nanotecnologa (ICN)

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Projects / Funding MAGNYFICO Magnetic nanocontainers for combined hyperthermia and controlled drug release (EU, 2008) Pulsos Magneticos Intensos Inducidos por paredes de dominio moviles: Aplicaciones a la dinamica Ultrarrpida (MICINN, 2009) Nanoantenna: Development of a high sensitive and specific nanobiosensor based on surface enhanced vibrational spectroscopy dedicated to be the in vitro proteins detection and diases diagnosis (EU, 2009). 2008 annual budget in M (including salaries) and an estimation when fully operating Budget 2008: 2 M Budget 2009: 3 M Budget forecast 2015: 4 M Campus de la Universidad Autnoma de Barcelona Facultad de Ciencias Edicio CM7 08193 Bellaterra Tel: +34 93 581 44 08 / Fax: +34 93 581 44 11 Contact person / e-mail Jordi Pascual / Jordi.pascual.icn@uab.es, icn@uab.es web: www.nanocat.org Summary: The ICN is a non-prot research institute, created in 2003 by the Catalan Government and the Autonomous University of Barcelona (UAB), who remain its patrons. The ICN works concurrently in Scientic Research (Nanoscience, primarily via European and national collaborative projects), and in Technology Research (Nanotechnology, in areas of internal expertise and co-development with private industry). In addition to its own research activities, the Institute also engages in collaborative research, dissemination, educational and managerial activities with other institutions such as universities, scientic institutes, ministries and private companies, at regional, national and international levels. Opening date: July 2003 Activity Areas Atomic Manipulation and Spectroscopy

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Inorganic Nanoparticles Magnetic Nanostructures Nanobioelectronics & Biosensors Phononic and Photonic Nanostructures Physics and Engineering of Nanoelectronic Devices Quantum NanoElectronics Nanoscience Instrument Development Laboratory Employees Actual: 100 (80 researchers, 20 administratives and technicians) Future: 150-200 total Infrastructure (from 100.000) The ICN has specialised facilities, some unique in Spain, including a powerful electron microscopy laboratory, FIB-SEM, electron-beam evaporators, nanoimprint lithographies, low and variable temperature STMs, magnetic characterization (Nano- MOKE, SQUID), AFM, SNOM, dip pen nanolithography, cryogenic and very low temperature cryogenic (< 20 mK) systems, X-Ray diraction and spectroscopy systems, Pulsed Laser Deposition (PLD) chambers, optical spectroscopy (Raman, IRFT, UV-VIS) and more. Projects / Funding Budget 2008: 3,8 M Budget forecast: 12 M

Centro de Investigacin en Nanociencia y Nanotecnologa (CIN2)

ETSE Campus UAB Building Q - 2nd Floor 08193 Bellaterra info@cin2.es Tel. 93 581 49 69 Fax 93 586 80 20 Contact person / e-mail Albert Figueras / albert.gueras@cin2.es web: www.cin2.es

Summary: Located in the Barcelona area, CIN2 is a key action for the development of Nanoscience and Nanotechnology in Catalonia and Spain, aiming to be an international referent of scientic excellence. CIN2 is a mixed center formed by the Consejo Superior de Investigaciones Cientcas (CSIC) and the Institut Catal de Nanotecnologia (ICN). This joint intellectual adventure spans from fundamental research in nanoscience to appplications of nanotechnology, interfacing with

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the industrial enviroment. We promote both local and international collaborations, and our research ranges from focused lines to transversal activities. Excellence and dedication are the pillars supporting the activity of this research center. Opening

Employees At this time the center has about 175 people, and within months the number will grow with the move to new building. The research sta represents the 80%, either employed or in training. The rest are administrative sta and technicians. Infrastructure (from 100.000) Dual System FIB-SEM XPS/UPS System ICN 05/08 X-Ray Difraction (capes primes (cu) I (co) ICN04/08 SQUID Mid-far IR Spectometer (ICN 08/08) EVAPORADOR DE MATERIAL MAGNTIC EVAPORADOR DE FEIX D'IONS STANDARD Axio Observer NANOMAN -01 DILUTION REFRIGERATOR AND MAGNET - MICROSCOPI PICO PLUS AFF/STM - DPN-0002-01 DPNWRITER TM NSCRIPTOR - Microscopi Pico PLUS AFM/STM - Pulsed Laser Deposition (PLD) - UV RAMAN (ICN010/08) - Multiview 4000 Microscope System - NANOMOKE2 - MICROSC. LT STM DE BAJA TEMPER - Microscopi STM 150 Aarhus Projects / Funding EURYI Quantum probes based on Carbon Nanotubes Prof. Adrian Bachtold, Leader of the Quantum Nanoelectronics Group at CIN2. UE. Specic agreement on management of technology transfer in the eld of biotechnology between CSIC and Fundacin Marcelino Botin. Laura Lechuga, Leader of the Nanobiosensors and Molecular Nanobiophysics Group at CIN2

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CIN2 exists as a center since January 2008. Since then, it has been temporarily located in several buildings around the UAB Campus. The permanent headquarters of the center are under constructions in the same Campus and will open by 2011. Activity Areas CIN2 (CSIC-ICN) counts with ve research lines. Theory and simulation at the nanoscale, Scanning probe microscopy and synchrotron radiation spectroscopy, Physical properties of Fabricated nanostructures, Chemical approaches to nanostructured functional materials and devices and Nanobiosensors devices. Each one of these areas has its sublines. At present, there are 13 research sublines of investigation. Atomic manipulation and spectroscopy Inorganic nanoparticles Magnetic nanostructures Nanobioelectronics & biosensors Nanobiosensors and molecular nanobiophysics Nanophononics and nanophotonics Nanostructured functional materials Novel energy-oriented materials Physics and engineering of nanodevices (pen) Pld & nanoionics Quantum nanoelectronics Small molecules on surfaces in ambient and pristine conditions Theory and simulation

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NOMAD - Nanoscale Magnetization Dynamic ERC-SIG-203329 (2008-2013). P. Gambardella, leader of the Atomic and Spectroscopy Group at CIN2 (ICN-CSIC). Budget 2008: 2 M .

ICFO-The Institute of Photonic Sciences

PMT-UPC

Avda. del Canal Olmpico s/n 08860 Castelldefels (Barcelona) Tel 93 553 40 01 Contact Person / e-mail: Gonal Badenes / Goncal.Badenes@icfo.es web: www.icfo.es

Summary: The Institute of Photonic Sciences, was created in 2002 by the regional Government of Catalonia, Spain - through the Department of Universities and Research - and the Technical University of Catalonia. ICFO is a research centre of excellence devoted to the study of the optical sciences, with the mission to become one of Europes foremost photonics research centres. The centre has a triple mission of frontier research, post-graduate education, and knowledge and technology transfer. ICFO collaborates actively with many leading research centres, universities, hospitals, health care

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centres, and a variety of private corporations worldwide. Opening: April 2002 Activity Areas Research at ICFO is organized in four wide-scope areas: Nonlinear Optics, Quantum Optics, NanoPhotonics and Bio-Photonics. Employees At present, ICFO hosts 17 research groups that work in 50 laboratories and one Nano-Photonics fabrication facility, all hosted in a 9000 sq.m dedicated building based at the Mediterranean Technology Park, in the Metropolitan Barcelona area. ICFO is currently expanding, thus by 2013 the institute will host some 350 researchers organized in 25 groups. Infrastructure (from 100.000) Optical and electron beam lithography Sputtering Thermal and electron-beam evaporation Plasma etching (RIE+ICP) Atomic Layer Deposition Spectroscopic ellipsometry

INSTITUTE OF NANOSCIENCE OF ARAGON

CENTERS

EDIFICIO I+D Campus ro Ebro, Universidad de Zaragoza c/ Mariano Esquillor, s/n 50018 Zaragoza Tel 976 762 777 Contact Person / e-mail Ricardo Ibarra (Director) / ina@unizar.es web: www.unizar.es/ina

Projects / Funding Nanophotonics for Energy Efficiencynanophotonics4energy (NoE, UE). Surface Plasmon early Detection and Treatment Follow-up of Circulating Heat Shock Proteins and Tumor Cells-SPEDOC (STREP, UE). Ultrathin Transparent Metal Conductors (CDTI, CIDEM, MICINN, industrial partners).

Summary: The Institute of Nanoscience of Aragon is an interdisciplinary research institute of the University of Zaragoza (Spain) created in 2003. Our activity is focused on R+D in nanoscience and nanotechnology, based on the processing and fabrication of structures at the nanoscale and the study of their applications, in collaboration with companies and technological institutes from dierent areas. Opening: The Institute was created the 6th May 2003 (DECRETO 68/2003, de 8 de abril, del Gobierno de Aragn).

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Activity Areas 1. NANOBIOMEDICINE The Nanobiomedicine line covers dierent aspects of the elds of the diagnosis and therapy, which involve the use of nanoestructured materials. Nanomaterials for Biomedical Applications - Inorganic Nanoparticles - Organic Nanoparticles - Nanostructures functionalization Nanodiagnostics - Magnetic Biosensors - Optic Biosensors - Contrast Agents for medical imaging Nanotherapy - Drug Delivery: (i)mobile vectors; (ii)fixed platforms; (iii) through biological structures (transfection, using Dendritic Cells) - Hiperthermia Nanotoxicity - Biocompatibility - Biodistribution - Citotoxicity From the research in this eld the new Spin-o NanoScale Biomagnetics (nB) has risen. It develops and commercializes technology and equipment for research in biomedicina. www.nbnanoscale.com Also, a new Spin-o, Nanoimmunotech was created in 2010. 2. NANOESTRUCTURED MATERIALS The aim of the Nanostructured Materials research line is to investigate and develop new materials and devices using bottom-up and

top-down approaches with applications of interest. The main research topics in this line are related to the preparation and characterization of several nanostructures, as well as with applications development: - Nanoporous Interphases: Microreactors and sensors - Hybrid Membranes - Carbon Nanotubes and Nanofibers - Nanocomposites - Organic and organic-inorganic hybrid Mono and Multilayers - Organic Polymers for Optical Applications - Safety in the handling of nanomaterials 3. PHYSICS OF NANOSYSTEMS Physical and chemical properties of molecules & materials at the nanoscale Spintronics Magnetism in thin films Materials and molecules structure with STM, AFM, MFM, HRTEM, UHRTEM microscopy Optic and electronic Nanolithography Nanofabrication through dual-beam MEMs and NEMs (Micro- and Nanoelectromechanical systems) Optical and Magnetic sensors XAFS espectroscopy quantums dots. Employees A sta of 120 researchers (61 Postdoctoral Fellows, 37 PhD Students, 15 Laboratory Technicians, 7 in Administration) are working at INA. Thanks to our qualied sta and our advanced instruments and infrastructures INA is a benchmark in Europe in the elds of Nanoscience and Nanotechnology.

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Infrastructure (from 100.000) The seven laboratories of INA are equipped with a state-of-the-art equipment. 1. Local probe microscopy Lab.: Atomic Force Microscope (AFM), Dip-Pen, two Scanning Tunelling Microscope (STM).

Total grant coordinated by INA: 888.636,00 Total INA grant: 222.000,00 Funded by: ERANET Leader: RICARDO IBARRA Title: Consolider-Nanotecnologies in Biomedicine Starting date: sept-2006/sept 2011 Total grant coordinated by INA: 4.500.000,00 Total INA grant: 800.000,00 Funded by: MICINN Leader: JOS LUIS SERRANO Title: Functional liquid cristallyne dendrimers: Synthesis of new materials, resource for new applications (DENDREAMERS) Starting-ending date: 01/10/2007-30/09/2011 Total grant coordinated by INA: 4.219.110,00 Total INA grant: 897.307,00 Funded by: European Commission 2008 annual budget in M (including salaries) and an estimation when fully operating The annual budget in 2008 was 8 M from research projects won in public competition plus also the annual budget given by the Aragon Government.

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2. Electronic microscopy Lab.: 4 Electronic Transmission Microscopes: TEM 200kW, High Resolution TEM (HRTEM) 300kW, Ultra High Resolution TEM (UHRTEM) 300kW with probespherical aberration corrected and UHRTEM 300kW with image objective-spherical aberration corrected. Two Scanning Electron Microscope (SEM). 3. Thin lms growth Lab.: Equipment for Pulsed Laser Deposition-Magnetron Sputtering (plasma PLD-Sputtering), and another Pulsed Laser Deposition. Molecular Beam Epitaxis (MBE). 4. Optical and electronic nanolithography Lab. Clean room 100 m2 class 10000 and 25m2 class 100.: Electronic Nanolitography with Dual Beam (Nanolab) 5. Characterization of nanostructures Lab.: X-Ray Photoelectron Spectroscopy and Auger Electron Spectroscopy (XPS-Auger), X-Ray Diraction (XRD). 6. Synthesis and nanosystems Lab. functionalization of

7. Biomedical applications Lab. Projects / Funding Leader: RICARDO IBARRA Title: Multifunctional Gold Nanoparticles for Gene Therapy (NANOTRUCK) Starting date: 01/07/2009-30/06/2012

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Centro Andaluz de Nanomedicina y Biotecnologa (BIONAND) / Andalusian Centre for Nanomedicine and Biotechnology (BIONAND)

BIONAND is the rst Spanish nanotechnology research centre entirely focused on nanomedicine. BIONAND is born to be the Spanish Nanomedicine reference centre. Opening: End of 2010 Activity Areas Nanodiagnostics, Thearapeutic Nanosystems, Nanobiotecnology

C/ Severo Ochoa Parque Tecnolgico de Andaluca (PTA) Mlaga, Spain Tel +34 955 40 71 39 / +34 955 04 04 50 Contact Person / e-mail David Pozo Perez david.pozo@juntadeandalucia.es david.pozo@cabimer.es web: www.bionand.es

Infrastructure (from 100.000) Cell Culture Facilities, Confocal and Electronic Microscopy Facilities, Espectroscopy Facilities, Flow Citometry Facility, Molecular Biology Core Facility, Animal facility. Projects / Funding 3 2008 annual budget in M (including salaries) and an estimation when fully operating 2.600.000

Summary: The Andalusian Centre for Nanomedicine and Biotechnology Centre (BIONAND) is conceived as a multidisciplinary space designed for fostering and promoting cutting-edge research in the eld of nanobiotechnology applied to human diseases. The centre is a joint initiative of the Regional Ministry of Innovation, Science and Enteprise of Andalusia, the Regional Ministry of Health of Andalusia, the University of Malaga and the Mediterranean Institute for the Advancement of Biotechnology and Health Research (IMABIS).

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International Iberian Nanotechnology Laboratory

- Nanotechnology applied to food industry, food safety and environment control. - Nanomanipulation, molecular devices, using biomolecules as building blocks for nanodevices. - Nanoelectronics: Nanofluidics, CNTs, molecular electronics, spintronics, nanophotonics, NEMS, and other nanotechnologies used to build nanodevices and system platforms to support the previous research topics. Employees Sta Currently Expected at full oper. Researchers 8 160 Administration 6 35 Technicians 6 55 PhD students 18 100 Total 38 350 Infrastructure (from 100.000) INL is currently purchasing and installing its main equipment. Among the projected equipment, INL include: Central Micro and Nanofabrication Clean Room: (Class 100 and 1000 ) with a 400m2 useful area, with an expansion capability to 600 m2. The gross clean room area (bay and chase) is around 1100 m2. The nanolithography area is specially designed to VC-E vibration specifications to accommodate two e-beam tools (10nm or better feature resolution). The optical lithography bay will include a direct write laser tool and mask aligners. Specialized labs with VC-E or better vibration specifications and particular EMI shielding requirements: Including imaging and

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Av. Jos Mestre Veiga, 4715-310 Braga Portugal Tel +351 253 601550 Fax: +351 253 601 559
Contact Person / e-mail: Jos Rivas (General Director) jose.rivas@inl.int web: www.inl.int

The International Iberian Summary: Nanotechnology Laboratory, a recently formed international research organization, is a joint research facility created by the Spanish and Portuguese governments to foster Nanotechnology and Nanosciences. INL is located in Braga, North of Portugal and it expects to achieve a research community of around 400 people at full operation. Activity Areas - Nanomedecine; drug delivery systems, molecular diagnosis systems, cell therapy and tissue engineering.

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Central Biology and Biochemistry facility: to provide support for groups developing biology and biochemistry activity (cell culture, DNA manipulation, microspotting, etc.). Additionally INL will have 22 to 24 wet and dry PI labs that will be gradually equipped (spintronics, NEMS, photonics, high frequency device characterization, nanomaterial synthesis labs, etc). Projects / Funding 1. Study of DNA interactions with inorganic nano-components, and how the morphology of generated self-organized structures can be regulated. The project includes tailoring design of bimolecular shell around nanoparticles and bio-linkers to control particle clustering and phases on surfaces and in bulk. Project in collaboration with Center for Functional Nanomaterials Brookhaven National Laboratory. New York, US. 2. Design, implementation and application of a new microscope for optical sectioning of live cells called the Programmable Array Microscope (PAM). Additionally this project includes the design and production of novel biosensors, obtained by combination of organic uorophores with Nanoparticles. These biosensors might later be employed as reagents to induce biological and physical eects

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characterization tools (HRTEM with spherical aberration correction, dual beam FIB/FEG, Bio TEM, surface analysis cluster(SIMS, XPS), shielded rooms. Central Scanning Probe Microscopy Laboratory: This laboratory will support SPM activity from standard imaging to advanced interdisciplinary applications and development of new techniques.

as well as for biosensing, exploiting photonic, electrical and magnetic elds in the PAM. This project is carried out in collaboration with Max Planck Institute for biophysical Chemistry in Gottingen, Germany. 3. Investigations in modern electron microscopy techniques such as Cs corrected STEM, Cs Corrected TEM, EELS, EDS, holography and others to the study of nanoparticles, nanostructures and soft nanostructures (polymers and bio materials). Studies include all aspects of image calculations and image interpretation. Project carried out in collaboration with the University of Texas at San Antonio.

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Valencia Nanophotonics Technology Center

Universidad Politcnica de Valencia Valencia Nanophotonics Technology Center Edicio 8F, 2nd oor Camino de Vera, s/n 46022 Valencia Phone: +34 96 387 97 36 Fax: +34 96 387 78 27 Contact Person / e-mail Javier Mart, Scientic Director jmarti@ntc.upv.es web: www.ntc.upv.es

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We are in a new building for the exclusive use of the center inside the UPV Science Park The building measures 3500 square metres with space for 100 professionals, including a 500 square metre cleanroom (class 10-100-10.000). The aim of the NTC and the UPV Science Park is to encourage regional development by transferring university research results to industry. The NTC oers an extraordinary technological potential and is dedicated to business development. Date of Foundation: The governing council of the Technical University of Valencia ocially approved the creation of the NTC on 24 July 2003. Research Areas - Optical Networks & Systems - Photonic materials & devices - Micro/Nanofabrication and Facilities The area Optical Networks & Systems is divided into six research lines: Optical Access and Next-Generation Networks Optical Networks Optical Signal Processing Lasers & Fibre-based Devices Microwave and Terahertz Photonics Frequency combs and DWDM sources The area Photonic materials & devices is divided into ve research lines: Metamaterials Biophotonics Optical modulators Nonlinear Silicon Photonics Polymer photonic devices The area Micro/Nanofabrication and Facilities is divided into four research lines: Nanofabrication Coupling and Packaging

Brief Overview The Valencia Nanophotonics Technology Center (NTC) is a research center inside the Universidad Politcnica de Valencia (UPV)). The center includes its own team about 75 researchers. Our mission is to establish leadership in Europe in the micro/nanofabrication of silicon structures for the development of nanotechnologies. Our photonics products are applied in sectors such as: optical bre networks and systems, biophotonics, defence, security, and photonic computation.

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Facilities & Equipment Photovoltaics Current and future personnel Current Personnel Steering Scientic Committee: 3 Management: 5 Human Resources: 1 Informatics: 3 Lab technicians: 6 Area Scientic Leaders: 4 Senior Researchers: 10 Junior Researchers: 16 Grant Students: 14 Nanofabrication: 13 Researchers associated to NTC: 5 Total: 9 persons in management and 71 persons in research Maximum Personnel Steering Scientic Committee: 3 Management: 6 Human Resources: 2 Informatics: 3 Technicians: 8 Area Managers: 6 Senior Researchers: 20 Junior Researchers: 40 Grant Students: 20 Nanofabrication: 20 Researchers associated to NTC: 5 Total: > 140 Most relevant equipments Lithography: Raith 150 e-beam direct writing, Nikon DUV stepper 180 nm, 8-inch wafers, TELmark8 Developer, TEL- mark8 Coater. Thin Film Deposition: Applied Materials P5000 and Centura Etch: STS ICP etch tool AOE Multiplex, AMAT

Most relevant projects, both running or approved in 2009. PROJECT TITLE: Improve Photovoltaic Eciency by applying novel eects at the limits of light to matter interaction.LIMA-FP7-248909. Financial Institution: European Commission. Coordinator: Universidad Politcnica de Valencia UPVLC. Participants: Universidad Politcnica de Valencia, UPVLC, Spain; Universita degli Studi di Trento, UNITN (Italy); Fundazione Bruno Kessler FBK (Italy); Agencia Estatal Consejo Superior de Investigaciones Cientcas, CSIC, Spain; International Solar Energy Research Center Konstanz ISC; Germany, Isofotn SA, ISO Spain; University of New South Wales, UNSW, Australia. Team Leader: Guillermo Snchez. Duration: from January 2010 to December 2012 Budget: 2.375.000 EUR (1.044.691 EUR UPVLC) PROJECT TITLE: TAILoring photon-phonon interaction in silicon PHOXonic crystals (TAILFOX) FP7-ICT Project 233883 Financial Institution: European Commission. Coordinator: Universidad Politcnica de Valencia UPVLC. Participants: UNIVERSIDAD POLITCNICA DE VALENCIA, UPVLC, Spain. OTTO-VON-GUERICKE-

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CENTURA and P5000. Chemical cleaning: FSI Mercury reactor, SEMITOOL organic solvent system. Physical Caracterization: HITACHI SEM S-4500 electron microscope. Evaporator: Pfeier Classic 500 EVG101 Advanced Resist Processing System Therma-wave Opti-probe 5220 Bruker VERTEX 80 FTIR (Fourier Transform InfraRed) Flip-Chip die attachment equipment SET FC150

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UNIVERSITAET MAGDEBURG, Germany. CATALAN INSTITUTE OF NANOTECHNOLOGY, Spain. NATIONAL CENTER FOR SCIENTIFIC RESEARCH DEMOKRITOS, Greece. CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE (CNRS), France. Team Leader: Alejandro Martnez Abietar Duration: from May 2009 to April 2012 Budget: 2.595.797 EUR (583.458 EUR UPVLC) PROJECT TITLE: CONSOLIDER ENGINEERING METAMATERIALS (EMET) (CSD2008-00066) Financial Institution: Ministerio de Ciencia e Innovacin Coordinator: UPV Participants: Universidad Pblica de Navarra, Universitat Autmoma de Barcelona, Universidad de Sevilla, Consejo Superior de Investigaciones Cientcas, Universidad de Mlaga Universidad, Politcnica de Madrid. Team Leader: Javier Mart Sendra Duration: from December 2008 to December 2013 Budget: 3.500.000 Euros (1.040.076,00 Euros UPVLC) Employees 54 Valencia NTC has a track record in leading European R&D Framework projects in FP5, FP6 and FP7 and also international contract with RTD organizations like European Space Agency, European Southern Observatory and European Defence Agency. Since 2000 NTC has coordinated 11 projects and has participated in 28 projects and networks of excellence. Annual Budget (M) Budget 2009 Personnel Costs: 1.989.683,34 Operation Expenses: 986.702,29

Indirect Costs: 595.277,13 Total: 3.571.662,76 Budget for 100% capacity Personnel Costs: 4.000.000 Operation Costs: 2.500.000 Indirect Costs: 1.300.000 Total: 7.800.000,00

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Centro de Investigacin en Nanomateriales y Nanotecnologa - Nanomaterials and Nanotechnology Research Center (CINN)

so called Controlled Design of Multifunctional Multiscaled Materials which comprises three research sublines: Modelling and Simulation Nanostructured Hybrid Systems Synthesis and Advanced Characterization of Nanocomposites and Bioinspired Materials

Parque Tecnolgico de Asturias Edicio Fundacin ITMA 33428 Llanera - Asturias Contact Person / e-mail Prof. Ramn Torrecillas San Milln / Director.cinn@csic.es web: www.cinn.es

Employees Personnel (currently): 46 Hired: 16 Training: 12 Civil Servant: 18 Personnel (Planned): 100 Infrastructure (from 100.000) Atomic Force Microscopy/ Scanning Tunneling Microscopy Electron Beam Lithography Single Cristal and Powder X-Ray Diffractometry Nanoindentator Hysitron - TriboLab Chemical Vapor Deposition (CVD) / Physical Vapor Deposition (PVD) Cryogenic dilatomete Spark Plasma Sintering Optical Laboratory (Holography) Elipsometer Hot Isostatic Press Projects / Funding IP NANOKER Structural Ceramic Nanocomposites for top-end Functional Applications. European Union. Sixth Framework Programme. Nanotechnology for Market (nano4m). European Union. INTERREG IVC. Desarrollo y Obtencin de Materiales Innovadores con Nanotecnologia Orientada DOMINO. MICINN.

The Nanomaterials and Summary: Nanotechnology Research Center (CINN) is a joint research center created in 2007 by institutional joint initiative between the Spanish Council for Scientic Research (CSIC), the Government of Asturias and the University of Oviedo. The CINN combines interdisciplinary research strongly competitive at international level with scientic and technological demonstration activities towards enterprises technologically advanced, and has among its main objectives the creation of new technology-based rms. Opening: 19th November 2007 Activity Areas The Nanomaterials and Nanotechnology Research Center is focused on one research line

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Annex I: NanoSpain Network

Research Topics Regional distribution of research groups Total personnel Members List

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Total Funding Evolution Total Funding Evolution Funding Origin

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Annex III: Publications / Statistics

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Annex IV: Spain Nanotechnology Companies (Catalogue)

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The catalogue, compiled by the Phantoms Foundation (coordinator of the Spanish Nanotechnology action plan funded by ICEX), and published in full version in the E-nano Newsletter (www.phantomsnet.net/ Resources/Catalogue_Companies.pdf) provides a general overview of the Nanoscience and Nanotechnology companies in Spain and in particular the importance of this market research, product development, etc. Note: only those contacted companies which provided their details are listed.
Edited and Coordinated by

The Phantoms Foundation is also coordinator of the Spanish Nanotechnology Plan funded by ICEX (Spanish Institute for Foreign Trade, www.icex.es) under the program Espaa, Technology for Life, to enhance the promotion in foreign markets of Spains more Innovative and leading industrial technologies and products in order to: 1. Represent the Scientic, Technological and Innovative agents of the country as a whole. 2. Foster relationships with other markets/countries. 3. Promote country culture of innovation. 4. Better integrate the Spanish Science - Technology - Company - Society system in other countries. 5. Generate and develop scientic and technological knowledge. 6. Improve competitiveness and contribute to the economic and social development of Spain.
Funded by

The Phantoms Foundation based in Madrid, Spain, focuses its activities on Nanoscience and Nanotechnology (N&N) and is now a key actor in structuring and fostering European Excellence and enhancing collaborations in these elds. The Phantoms Foundation, a non-prot organisation, gives high level management prole to National and European scientic projects (among others, the COST Bio-Inspired nanotechnologies, ICT-FET Integrated Project AtMol, ICT/FET nanoICT Coordination Action, EU/NMP nanomagma project, NanoCode project under the Programme Capacities, in the area Science in Society FP7) and provides an innovative platform for dissemination, transfer and transformation of basic nanoscience knowledge, strengthening interdisciplinary research in nanoscience and nanotechnology and catalysing collaboration among international research groups. The Foundation also works in close collaboration with Spanish and European Governmental Institutions to provide focused reports on N&N related research areas (infrastructure needs, emerging research, etc.). The NanoSpain Network (coordinated by the Phantoms Foundation and the Spanish National Research Council, CSIC) scheme aims to promote Spanish science and research through a multi-national networking action and to stimulate commercial Nanotechnology applications. NanoSpain involves about 310 research groups and companies and more than 2000 researchers.

The Spanish Institute for Foreign Trade ("Instituto Espaol de Comercio Exterior) is the Spanish Government agency serving Spanish companies to promote their exports and facilitate their international expansion, assisted by the network of Spanish Embassys Economic and Commercial Oces and, within Spain, by the Regional and Territorial Oces. It is part of the Spanish Ministry of Industry, Tourism and Trade ("Ministerio de Industria, Turismo y Comercio").

Contact details Phantoms Foundation Calle Alfonso Gomez 17 28037 Madrid (Spain) www.phantomsnet.net

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Annex V: NanoSpain Conferences

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Annex V: NanoSpain Conferences As a direct and most eective way to enhance the interaction between our network members, a rst network meeting was organised in San Sebastin (March 10-12, 2004) with around 210 participants registered. Due to this success, the network decided organising its annual meeting, Barcelona (March 14-17,2005), Pamplona (March 20-23, 2006), Sevilla (March, 12-15, 2007), Braga-Portugal (April 14-18, 2008), Zaragoza (March 09-12, 2009) and Mlaga (March 09-12, 2010) with a similar format. Its objective was also to facilitate the dissemination of knowledge and promote interdisciplinary discussions among the dierent NanoSpain groups. In order to organise the various sessions and to select contributions, the meeting was structured in the following thematic lines, but interactions among them were promoted: 1. Advanced Nanofabrication Methods 2. NanoBiotechnology 3. NanoMaterials 4. NanoChemistry 5. NanoElectronics / Molecular Electronics 6. Scanning Probe Microscopies (SPM) 7. Nanophotonic & Nanooptic 8. Scientic infrastructures and Scientic Parks 9. Simulation at the nanoscale

In 2008, Spain, Portugal and France (through their respective networks NanoSpain, PortugalNano and CNano GSO) decided to join eorts in order that NanoSpain events facilitate the dissemination of knowledge not only in Spain but among the dierent groups from Southern Europe.

A list of all institutions involved in the organisation of the Nanospain conference series, is provided in the next table:

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Annex VI: Maps for relevant Spanish initiatives

Emerging N&N Centers in Spain. Unique Research and Technology Infrastructures supporting nanotechnology research / ICTS. Other initiatives (networks, platforms, regional programmes, conferences, etc.) related to nanotechnology promotion.

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